If
0;
f~
GROUP THEORY
THB APPLICATION TO QUANTUM MECHANICS
PAUL H. E. MEIJER
17Ie Clltllollc UniNriity 0/ AIIterlt:G, Wash'IIgton D.C.
EDMOND BAUBR
Laboratoire de Chi",. Physlqw, Pari3
1962
PUBLISHERS :
a division of
INC.  NEW YORK
SONS~
v/H
GJtQN1N9EN
PREFACE
Seldom has an application of socalled pure mathematics to mathematical
physics had more appeal than the use of group theory to quantum mechanics. Almost every student in this subject, after going through the necessary
theorems, felt the satisfaction of overlooking a broad field,) Inastering it in
its complete generality, as an award to his efforts.
In recent years the availability of tables of coefficients has increased the
applicability of many ideas introduced one or two decades ago and the number of papers applying the results of representation theory has been steadily
increasing.
The application of group theory to problems in Physics can be classified
in two types. As an example of the first type we mention the considerati<;lns
based on the symmetry of a crystal used to reduce the 6 by 6 stressstrain.:matrix (the generalization of Hooke's law)~ An example of the same
type is the heat conduction tensor in a crystal. Instead of nine components the
number of different elements is reduced by the symmetry of the crystal and
still further reduced by the Onsager relations (which are based on microscopiq time reversal). Still another example of the first type is the set of piezoelectric constants .
T~e second type of problems are those eigenvalue problems where the
differential equation or the boundary are of such a geometric nature that
certain rotations or translations leave the. problem unchanged. In this case it
may happen that the eigenvalue connected with the solution of the problem
is degenerated; that is, more than one eigenfunction belongs to the same
eigenvalue.
The central problem of the book is the study of this second type through the
transformation properties of these eigenfunctions. In the first cases the application of "group theory" is hardly more than the application of symmetry
considerations. In the second case the application of group theory, or actually the application of representation theory, is a much tn<?re essential
matter. The general idea of the transformation induced in function space
by a rotat.ion (or translation) in configuration space as explained in Chapter 4 is not only useful in Qlla.nt.wn. mechanics but in any other eigenvalue
\
PREFACE
vi
the
I would like to quote from the introduction to tl;le first edition the following s"4&tement: 'The pages that follow are simple introduction. having aa
main~8oal to familiarize the reader with some new concepts and to permit
him to read the oriainal papers orWell and Wigner with less difficulty."
I ,_ouId like to thank Mrs. Peretti, Drs. Morrison and Barry and Mrs.
Mielczarek for their cooperation.
J
CONTENTS
CoNTBNTS ....
CHAPTER. 1.
1.
vii
1.2.
1.3.
1.4.
1.S.
2.
. .. .
Tranaformation of coordinates..
.. ~ .
Linear mapping of the space at. on itself (linear transformation)
Composition of mappinp. Multiplication of matrices ....
fA
.......
Inverse matrix . .. . . . . . , .
~
1.6. Transformation or a mapping or projectionmatrix by a chanp
dinates (similarity transfonnation)..
. . . . ~ " ~ .
Euclidean and unitary spaces. .
. . ,. . .
2.1. UQitary metric . . ~ . . .
~ ~
2.2. Unitary transformation . . \'; *
2.3. "Bilinear forma and Hermitian matrices
. . .
2.4. Goneralization of unitary space into bra... and ket spaces ~
R~uction to main axes . . . . " ~ , ~
3.1. Dialonalizability. .
c
'I
..
..
..
..
..
01 coor4
6
6
8
8
...
..
4t
3.
..
..
..
9
11
11
.0
4"
I.
..
..
..
fl
'"
..
..
..
..
"
...
<!
..
:ot
:I;
,.
"
..
CHAPTBlt 2..
1.
..
,.
1
1
1
2
3
4
12
14
14
IS
l'lJ
16
17
19
19
21
21
Wa"v'es ~ . .. = ~
1.1. Classical waves . . .  . . . .
1.2. Quantum mechanical waves
.....
1.3. The free particle . . , .
<
vii
29
29
30
31
viii
2.
3.
4.
s.
6.
7.
CONTENTS
The Schrodinger equation .
2.1. 8.chrodinger equation .
2.2. The nparticle problem
Angular momentum . . .
3.1. Operator . ~ . . . . .
3.2. Operators and groups .
3.3. Commutaiion relations
The postulates of quantum mechanics.
..
Time dependence of a state and of a physical
5.1. General theory
I. ~ . . . . .
5.2. Heisenberg representation . . . . . . .
Transition probabilities and radiation theory.
Perturbation theory . . . . . .
. .
7.1. Formulation of the problem . . . . . .
.
7.2. Nondegenerate problems
7 . 3. Degeneracy . . . . . . . .
7.4. Quasi degeneracy . . .
7.5. Application: diatomic molecule . . . . .
b
CHAPTER 3.
1.
2.
3.
s.
6.
32
33
33
34
34
35
36
37
. ., .
observable.. . .
40
40
42
.
., .
. . . . . . . . .
. . . .
45
47
47
48
49
52
56
GROUP THEORY
58/
. . .
. . . . .
. .
59
59
61
62
63
64,
64
65
66
66
67
68
69
9'. (symmetric
70
70
71
72
72
72
72
74
74
CONTENTS
ix
7.
Reducibility of representations . . . . . .
7.1. Invariant subspace . . . . . . . . . . .
7.2. Complete reduction or decomposition
... .
1.3. Reduction of the unitary matrices of a group into their irreducible parts
7.4. Ex.a.mple . . . . . . . . . ~ . . . . . . . . .
7.5,. Finite gI"OUpS
............................ ~ .
8. Uniqueness theorem. The decomposition of a given representation (II from
a group ~ into irreducible constituents is only possible in one way.
.....
9. Schur's lemma and related theorems
10. Characters of a representation . . . . . . . . .
10.1. Definition . . . . . . . . . . . . . . . . . . . . . . . . .
10.2. The number of irreducible representations of a finite group. . .
10.3. Regular representation of a group
. . . . .
11. Orthogonality relations (finite groups). . . . . . . . . . . . . .
11.1. General formulas . . . . . . . . . . . . . . . . . . . .
11.2. Application to the characters of irreducible representations
11.3. Class..Space . . . . . . . . . . . . . .
12. Sum of a class; projection operators . . . . . . . . . . . .
12.1. Definition of the sum of a class; structure coefficients.
12.2. Character tables . . . . . . . " . . . . .
12.3. Projection operators (idempotent elements) .
13. Repre~enta~ons of the permutation group.
13.1. Youngtableaux. . . . . . . . .
13 . 2. The P" Qoperations; idempotents . .
13.3. Irreducible representations . . . . .
Appendix 3.1. . . . . . . . . . . . . . . .
CHAPTER 4.
..
..
75
75
76
77
77
80
81
82
85
85
86
87
89
89
92
93
94
94
95
97
100
100
102
104
106
THEOREM
110
110
110
111
112
113
113
114
120
121
122
124
126
CONTENTS
CHAPTml 5.
!'I,
149
5.1. Kinematic coupling of two systems with sphorical sJllbDOtrY.
14'
S. 2. Product of two representations . . . . . . . . . . . . . . . . . .
.. 150
5.3. Reduction or the diJect product of two ropresentations. Group _. I I
an example. ClebschGordan formula . . . .
~
1'2
5.4. Total angular momentum . .
. .. . .
153
5.5.. Helium atom without spin
. " . .. . . . . . . .
1~
6. The electron spin .
156
6.1" UhJenbeck and Goudsmit hypothesis
" " .. .
J"
15.
6.2* Translation in quantum theory (pauli) " . . . . . .
6.3. Applications . . . .
. .. .
. .. . . . . . . . . .. . IS9
6.4. Complex atoms
..."........"....
. . . .. .. . . 160
7. Selection rules. . . . .. . . . . . . . . . . .
. .
162
8.
Parity or reftection character. Approximate selection rules ........." . 164
8.1. Parity; Tho rule of Laporte . . . . . . . .. . ....
. .. ..
164
8.2. Approximate selection tules . . . . . . . . . . . . . .
166
9,' Stark effect. Anomalous Zeeman effect. Line componetlta iDteDsity. ..LaacW
166
splittin, factor. PaschenBack eaect ..
. .. . . . .
9.1. Goneral theory
. .
" .. . . .. 167
9.2. Intensity or components . . . . .
.. .. . . . .. . . 168
169
9 . 3. Landefactor . .. .. . . . . . . . . .
. " .
Appendix I. The connection between a formal set of basis f\mctions aad the spherical
harm.onics . . . . . . . . . .
172Appendix II.. Construction of the irreducible representation of the 1l'01Ip _ . . 173
Appendix Ill. Proof of the formula (5.34a) . " " , . .. . . . " . .. . ... 171
1.
&
..
..
..
..
..
.......
...
fI
..
..
&
..
..
.....
..
..
"
It
..
Ii
CHAPTER
1.
2.
3.
4.
6.
"
..
..
"
. ..
. . .. .. ..
..
.
184
187
189
193
CONTENTS
23.
4.
S..
6.
7.
8.
9.
2.
3.
4.
5.
It
199
202
. .
.
.
198
206
208
..
..
"
.. ..
."
210
213
217
220
220
223
FINITB GROUPS
6.
.. ..
CHAPTER 8.
I.
. ..
.
.
Outline . . . .. .. ..
..
.. .. .. . .. .. . .. .
Crystalloaraphic point groups versus pnal point groups . ..
, ..
..
Space Iloups .
.. .. .. . .. .,
..
.. ..
Pure traaslatiollS " ..
" ..
" "
.. .. ..
Bloch theorem .. .. .. . . .
. .. "
Reduced wave vectors "
"
" "
"
"
.
.
..
Little groups, W.B.S. method"
"
".. .. . .. .
9.1. Little a;roup theory .. . ..
.
.. ..
hOBI . . . .
228
. . . "
233
233
." .
symmetry
II
...
II
"
237
......
. . . .
. . .
. .
~
. . . .
. . . .
. . . . . . . .
244
245
249
~3
. .
2'3
256
" ..
2S9
241
259
261
264
. ..
261
273
217
SYlTDlATIC BmLIOOIlAPHY
279
CHAPTER 1
VECTOR SPACES 
UNITARY GEOMETRY
= 0,
(1.1)
In ordinary space, n = 3, the el are unit vectors laid out in three arbitrary
directions, the coordinate axes, and Xi' the components of the vector x, are
real. In quantum theory the quantities considered are in general complex;
thus one is led to take complex
x,.
If at,. is a vector space spanned by n basis vectors ef, let us select n other
independent vectors ei. From (1.1) the e~ will be linear combinations of the
ei (as all vectors of 8lra are). Thus we will have
(1.2)
where S
11
X,
GEO~iETRY
and
[eh. I, 1
"
=:; ' 
Xi~! ;: ~"
Xk e"
L
It
'
=v
L Xkeisik,
u:
from which
(1.3)
or
(1.3a)
Notice the difference between (1.3a), the transformation formula for the
components of the vector, and (1.2), the transformation of the unit vectors.
One traDsro~tion is the transpoaed inoerse of the other.
The notion of a vector can be genera1ized to tensors, quantities that ~ave
of the
To each vector x of It,. let there correspond a vector of the same space
., == Ax defined in the same coordinate system by its components;
Yi =
Lk
Qlkx/C;
Ax =
L sJafkxk'
(1.4)
i. It
c, = 1.
h
tt... DIl\1ENSIO"NAL
Ch. I, Ij
VECTOR
SPACE~
One can map' It,. on another space &lift where m may be different from 11 and
in this case, the matri~ A is rectangular.
The mapping, A, of Ut n' on itself transforms a vector which is originally
identified with one of the basis vectors ek; into 'Ik == Aek and since ek has the
components D,. lone finds in accordance with (1" 1),.
(1.4a)
Note the identity in form of the equations (2.1) and (l.4a),' A change of
coordinates is a type of mapping limited to the basis vectors only.
The mappings are transformation operations on the ndimensional space.
Their symbols A are operators acting on the vectors of this space in order to
transform. them into other vectors. These operators are analytically expressed
by matrices of the degree n. The mathematical problem presented by quantum mechanics is to generalize the properties of these operators to the case
where n is infinite.
1.4.
CO~fPOSITION
OF MAPPINGS.
~fULTIPLICATION
OP MATlUCES
ex .
The successive operations are carried out in the proper order by reading
from the right to the left in this equation. This rule will always be applied in
the: calculus of operatorso Equation (1.4) gives us
z,
=:
'"
that is
(1.S)
The matrix C is obtained by the usual multiplication rule of determinants.
The same result is also found when the mappings are carried out from one
space to another provided that the number of dimensions lend themselVes'
to it, as we shall see beiow.
It is convenient to represent a vector :t by a matrix X, where all the components are arranged hI a single column (the first one for example) and where
lOne has obviously
VECfOR SPACES 
UNITARY GEOMETRY
[eb. 1, 1
all other places are filled with zeros. Without difficulty one sees, from (1.4)
and (1.5) that the formula y = Ax becomes
Y = AX.
(1.4b)
...
{C]
t
II
1
Pig. 1.1.
(1.3a)
xl=La;1Yk or
X=A~lY=AIAX.
= A lA =
I =
(t?ik),
(1.6)
that is
(1.6a)
1.6. TRANSFORMATION OF A MAPPING OR PROJECTION MATRIX BY A ,
CHANGE OF COORDINATES (SIMILARITY TRANSFORlvIATION)
Let e, be the initial system of basis vectors in which we will carry out the
transformation x + y = Ax. Now let us change the basis alld let e~ be the
Ch. 1, 1]
y;
new basis vectors and xi, the new set of components of the vectors % and
y. The mapping or projection A, that is to say the correspondence between
the vectors % and y, is expressed in the second coordinate system by a
matrix A' such that
(1.4c)
" = A'x'.
x,
l' =
x; = Las; x.
S1"., == A%,
== S.x',
that is
(1.7)
Twb transformations A and A' are said to be equivalent if they are related
by an equation of the type (1.7), where S is au arbitrary transformation,
having an inverse. They go over into each other by a chanse of axes.
, As a simple example let us consider the operation in which every vector of
a th.reod:imeasional vector space tR3 is rotated throup an anaJe 8 .. 45
around a given axis II coinciding with e3 This operation can be expressed by
y == Ax where the matrix A is given by (compare Fig. 1.2&):
= (: :
'~)
001
(8
= iJ2).
S=
(~0 1~ i),
0
VECTOR SPACES 
UNITARY GEOMETRY
[Cb. 1, 2
we obtain the new basis vectors el, e~ and e; indicated in Fig. 1.2b. The
4Sopera:tion described above is now given by y' == A' x' where
A' =
(~
o
1
o
B)0 ,
B
\ ...............
",
:~
.... _I
\
\
.......,
\:
\ I
\~
.
;
.
,6 ,........
, ..........
.,/
45
... ....
':/5
\ J
\,
"
Fig. 1.2a
Fig. 1.2b
Fig_ 1.2. Tho . operation "rotate every vector of the 3dimensional space . . through, an
&nile 8 1=: 45 0 around a given axis a" performed in two different systems of reference.
UNITARY METRIC
_,ric
x2 =
i: 9a x ,x" 1.
ik
1 A metric in which. go Is nondiagonal is not very often used, at least in the c:ase of
CODStant coe.IIi.deDtB. A nondiagonal metric geometrically interpreted means that we have
an oblique coordinate system. In this case tho projections perpendicular and parallel to
the other coordinate axes are tile co and the contravariant components. If tho vectors are
functiOns (compare 1.4). a DOD...iialonaI metric meaDS a set of nonorthogonal wave
functions, which are used in some exceptional cases, for instance the Orthogonali.zed
Plane Wave method in solid state physics.,
In general gQ may be functions o'fthe coordinatss Xl,~ Here alr~~dy in the diagonal case
Ch. 1, 2]
EtJCLIDEAN
<l~~ND
UNITARY SPACES
xl. ;: (x x)
== L, XiXi'
(1.8)
i= 1
= L, XiYi
= (y
x)*.
(1.8a)
These equations show that the axis of a unitary coordinate system are
orthogonal tmit vectors; their norm. is equal to one and the scalar products
of any pair are zero because the components ell and ek~ of' e,and e.. are 6" and
~'d respectively. 11lus we have:
(1.8b)
One verifies at the same time that the component Xi is equal to the scalar
product of the vector x and the unit vector e,:
(l.8e)
because the components of , are real.
In 1.4 we mentioned that vectors may be considered as special (rectangular) matrices. In order to obtain invariants, i. e. onebyone dimenst9nal
matrices, like the scalar product (1.8) and (I.Sa) one matrix has to be of the
onecolumn type, the other matrix of the onerow type. If we write equation
one must distinguish between. co and contravariant components (MOBIB aDd FIIHBACB
(1953) pp. 30 and 44) .. A simple example ora variable orthogonal metric is a...,Jar c0ordinate ~~. The most sencral fOmi, where 6,. are functions and aondiaaonal, is.,aod in
the gcmera1 theory or relativity. (Compare "I. H. WBYL [1922) sections 2. 3. 4.and 11.)
y.7~ would like to remind thO reader that there are linear spaces used in mathematicS in
wpiqt 114.' metric is introduced, for instance,. the groupalgebra mentioned in Chapter 3,
10,'.
VEcrOR SPACES 
UNITARY GEOMETRY
reh. 1, 2
(1.8) in matrix notation, the lefthand side of the product becomes the
transpose of the complex conju,ate of the righthand side.
2.2. UNITARY TRANSFORMATION
A unitary transformation is a change in coordinate system, it is a transformation from one unitary system e, to another ~;. If x, and x; are the
components of an arbitrary vector x in the two systems, one must have
x x == Lxix,
, == L, x;*x; ,
hence this requires that the coefficients in (1.3) obey the following restriction,
Lxix,
=: L (SIkX~)StlX; == L x~X;(L S:Sn),
,
i. k. ,
k, I
that is to say
or using
(1~6a),
..
Slit
==
1
S,d
satisfy .becomes
5ts = I.
Sf ::::: S 1 ,I.e.
(1 ,9)
L x:aIkY~.
(1.10)
i, k
X,
and Yt . 1
Prom its/Very definition this form is invariant, that is to say it does Dot cbanaeunder a
unlttll7coordiDate transformation. Hence if ODe considers theJt, as covariant components
aDd the x: u contravariant components, the matrix A is a mixed ten80r of the second order
in unitary space.
1
Ch. 1, 2]
xAy::Ax"
(1.11)
thus
and finally
ait  a*
lei'
A = At.
(l.lla)
One can verify without any trouble that the quadratic form Ax % is real if
and only if A is Hermitian. The expression x % is always real by virtue of its
definition (1.8) and obviously ;c. 1 is Hermitian.
2.44. GBNERALIZATION OF UNITARY SPACE INTO BRA AND KET SPACES
V,;,.
10
,lEcr'OR SPACES 
UNITARY GEOMETRY
[Cli. 1, 2
I
the adjoint vector in
it
>= LXIii);
t
or bra space is
<I=: LXi(il,
i
XiXi
since the brackets (iii) are all equal to one as Ii) was a unit ket and (If was a
unit bra and we assume for simplicity that the scalar product of two different
<iIi> = 0,
i:p j.
An operator that establishes a projection in ket space can be fully characterized by the mappings of all the unit vectors,
Aji) =
L aljli),
j
and if we are interested in the scalar product of an arbitrary bra <il and the
projected ket Ali) we obtain a set of numbers.
<iIAli)
aijvli) = au
<iIA = aJi(il
(we write
A to the left
result, one has to remember, however, that the action of this operator is
from right to left). The scalar product with an arbitrary vector in ket space
gives again a set of numbers that characterize the operation completely.
(jfAli)
:=
ail
A'
The same index in the "opposite" positions means a sum over that particular
Ch. 1, 2, 3]
11
Finally we want tf) mention a quantity which consists of a ket and a bra:
li)</JI . This is not a number, but an operator. Its matrix elements between
the bra (il and the ket Iv) are
0Ii><JLI11) ==
~ij~/tV"
. . . . . ,
o 0 ... IX,.
sts
:8
I.
(1.13)
VECfOR SPACES 
12
UNITARY GEOMETRY
[Ch. 1, 3
We would like to end this section with a short note on the diagonalization
of matrices in general. The question "Which class of matrices can be fully
diagonalized7", is usually not treated in physics, hence the mathematical
techniques in physics sometimes create the misunderstanding that all matrices can be diagonalized.
, A normal matrix N is a matrix that commutes with its Hermitian conjugate:
NNt  Nt N = O.
(1.12)
An arbitrary matrix can always be brought into a form in which lutlf the
offdiagonal elements, Le. at one side of the diagonal only~ are zero 1 ~
If we have a normal matrix, the relation
(~1
..
::
..
: : :)
'
oormal form .
. Except the case in which the ellipsoid or dielectric constanta is an ellipsoid of revc>lu..
tion~
Then the two main values of the dieloctric constant are equal (a degeneracy)" Thus
only one main direction is determiDed; it is normal to a plane in which the two othor
axes can bo chosen arbitrarily!
Ch. 1. 3J
13
y == Ax = ax,
(1~14)
where (X is a constant.
Writing the "components" of this vector equationt we obtain n linear
homogeneous equations of the form
(allA)
Det IAA.It
I
(a22 A)
I = o.
(a.A.) I
at2
.. ..
ala
42,.
==
..
..
II>
..
..
..
II>
..
..
(1.15)
..
This equation has in general n roots.l ::: (Xl II . . . . ,. (which may be distinct
or not) to which correspond the 11 directions of the axes given by' equation
(1.141.). We know only the directions of the vectors :I but ftot their'magnitude
becaUse (1.144) determines omy the ratios between the oomponents. The
roots' , of (I. IS) are the eigenvalues, propervalues, or characteristic con..
stallts of the matrix A. They are real in the' Hermitian case; in the unitary
case 'their absolute value is 1. The are the eiaenvector. or principal direetiollSa~ . When (1.1S) represents a multiple roOt of order P(<<l  2 :::e ~
er
This name oriainates from a PrQblom in astroD9Jll)', where a siluilar "Iuation deter. .
one
0
..
:
0)
o au .
() .. ..::: .
<<1 }~
t.
~:
a", .
~~
VEcrOR SPACES 
14
UNITARY GEOMETRY
[eh. 1, 3
form a subspace
of p dimensions in which the direction of the axes is not determined. (See
(X%
= B'A'.
Now we will show that the condition is sufficient: let us suppose that AS =
BA and let us make a transformation of coordinates such that 8 is diagonal:
We have
If
{J, ~
p",
QUe
== O.
So ~ fiIld that A is a Itep'WiIe matrlxt of which all the terms are zero,
cxce~ those which are", situated on the main diagonal, or those inside certain
squar~ that share the diagonal; they correspond with the case in which
p, "ll"e These squares are eaGh related to a subspace \ll in which the
~pal directions of the matrix B are undetermined (the matrix posseasoa a
cirtuiar, spherical, or hyperspherical symmetry)_ One may finaDy choose
these undetermined axes in such a way that A will be completely diagonal
3.4. INVAlUANCE OF A SBCULAll EQUATION
+
A' .. SlAS;
(1.16)
Ch. 1, I 3, 4]
15
FUNCI10N SPACE
Let A = (aft) be a matrix, the trace is then the sum of all the diagonal
elements
,.
Tr A ==
,=2: ail
(1.17)
To prove that the trace is invariant we shall write equation (I. t S) in the form:
(1.17a)
16
VECTOR SPACES 
reb.
UNITARY GBOMETRY
1, 4
for the same values of x there corresponds a distinct vector which is the
geometrical representation of that particular function.
Normally the functions in which we are interested depend on continuous
variables. So we have to go over to the limit in which the number n of dimensions of the function space becomes infinite. In such a case one may
consider the value ~ of the variable x as an index and. say that J/J(e) is the
component of a veetor '" along an axis characterized by the index ~4I For
functions of several variable., such as "'(x~ Yt z) the set x, y, z constitutes one
single index and the function space shows the same properties as those with
a single variable.
In the next section we will reason maiDly by analolY and be satisfied by
indicating now and then the mathematical difficulties. We will always assume
that conditions of convergence are realized.
4.2.. SCALAR. PR.ODUCT'; NORM
X, = '1l:x:Yill
and y has
fJ
(I.Sa)
(t/I tp)
=tL l ",*{Xt)!p(x,,).
(1/1 .) =
.,,*(x)cp(x}dx.
(1.18)
Thia iatearal is the _ar product of two /unctiDNI ';(X) ' and 'P{x). The
wave function in quantum mechanics depends on the coordinates of the
particles Xl , Yl, %1, X2' , z,., the domain D is the, finite or infinite configuration space in which we will indicate the element by dt == dx 1 ., dYl
dZ l dx2
II
=
Iv",.dt.
(L1Sa)
( 1.19)
17
FUNCflON SPACE
Ch. i, 4]
We will assume that all the functions which we will consider make the
integrals converge, whatever the domain D is, even if it is infinite. These
are called square integrable functions.
4.3. FOURIER SER.IES. COMPLBTE SETS OF ORTHOGONAL FUNCTIONS
are
;III:
(tp" P,.)
tp,.
.
= 1 f+ eu'~ei~dx
== 6
ma ;
2" _.
= (21t)"~*ehU:;
((i",
= (2n)iet m.x.
Jim
Jt+ co
J
D
(1 ..21&)
_
I it means the absolute square. So we deaJ with an unlimited approximation In the mean
on the domain D or C(Jnv~'gence in tit, lMaR. It is Dot necessary that ~)Plltp" is converscnt.
The ronnulas (1.22) and (1.23)' can result just as
trorn tbis detlnition as from our
restricted definition. AD the calculations, including those in perturbation theory in
Chapter 2. can be pttIonnod by makin, use of the ri,OtoUl deAnition(1.21a). We have
preferred to sacriftce pnerality ip. order to simplify the ar~ents.
wen
18
VECTOR SPACES 
UNITAR,\' GEOMETRY
(eh. 1, 4
~lA:'
(1.20)
the integrals being extended over the domain D. Second that all the continuous
functions which occur in the applications in physics can be expressed in this
domain by a series development of the form
(1.21)
k being an index which is allowed to talce all integer values between 0 and 00
or ~tween  00 and + co (as in the case of a series of expon~ntials). If one
cotnpares (1.21) with (1.1) and (1.20) with (1.8b) one sees that these equatioris can be expressed in the following geometrical language:
~. A complete system of orthogonal functions establishes a unitary system of
coordinates which spans completely the function space. The p" or the
Fourier coefficients are the components of the vector t/I in this system. These
unitary axes establish, by their very definition, a denumerable set. Therefore,
they permit Feduelion of th~ properties oftbe functional space to those of a
space with an infinite denumerable number of dimensions.
If we form the scalar product of "', and", and take (1.20) into account,.
we obtain
(1.22).
a wenknown formula from Fourier which allows us to calculate the coeftl.
dents
axis
19
OPEllATORS
Ch. 1, 4, 51
(t/I .;) =
Lfpi"'!fJk,t/llr.d~ = L PiP,
(1.23)
It
If one can show that this relation is correct ror an arbitrary continuous
function, one is sure that the set of 1/1, is complete. The choice of orthogonal
functions that span the function space depends essentially on the problem
that is studied. There is an infinite number of possible choices, whether the
domain D is finite or infinite. The different complete sets can be derive4 from
each other by a change of coordinates or unitary transformation (compare
2.2).
5. Operators
'.1.. TRANSFORMATION
LINBAR OPERATOR
==
(d/dx)t/I(x).
of
20
VECTOR. SPACES 
UNITARY GEOMETRY
[eb. 1, S
(1.24)
We write:
where At/I.J the function "" transformed by the operator A, can be developed
itself in a serieI of fundamental functions '" 1, '"2' with Fourier coefficients Ga:
(1.25)
From which we find that:
.,,' at
<l/I, Al/I,) 
fl/IiAl/Itd't t f
=
l/Itl/lJaJtd't
= all:;
(1.26)
==
L, .;,u"'.
C{J,
(1.27)
21
OPERATORS
Ch. 1, 5]
The arguments of 1.6 are still valid under the condition that we give the
infinite matrices, with which we are dealing here, convenient convergence
properties. We will obtain for the expression of the transformation A in the
coordil1ate system lPk'
A' = U 1 AU.
(1.27a)
5.2. BILINEAR FORMS. HERMITIAN OPERATORS
(1~25)
we obtain
i~ k f
..
(1.28)
i, k
L f l/!:atiP'iYIl/!,dr: = LYka~M~
11:, i, i
(1.29)
I, t
constant:
(1.30)
The functions found in this way are the eigen/unctio1t8 or eigenvectors of
the operator .t\; the numerical values eli its eigenvalues.
22
VECTOR SPACES 
UNITARY GEOMETRY
{Ch~
1, S
The solution of this problem for a space with a finite number of dimensions
is relatively simplo ,at least in principle ( 3) and can be done by purely
algebraic methods. In function space, on the contrary, complications and
considerable difficulties appear and rigorous discussion of the equation
(1.30)1 has not been completed by the mathematicians.
The problem of finding (%, is algebraic, differential, or integral according to
whether the operator A is algebraic, differential, or integral. The Schr6dinger
equation (2.15) is a particular case: The Hamilton operator to which it refers
is a differential operator. Discussion of physical problems presented by
quantum. mechanics has lead to a better understanding of equation (1.30)
since the work of Hilbert .
Depending on the nature of the operator A and on the size of the domain
D, which restricts the variables on which the function l/I depends, we are
dealing with two different cases.
1. The easiest case arises when the square summable solutions of equation
{193l]~
See, for example, ltlLBD.T and CoURANT (1930]. Chap.. Sand 6 or P. lvi. Mi.~ a.ad.
FuIlJlACH !19S3] p~ 727 and p~ ilSi>
H.
Ch. 1,
S1
OPERATORS
23
and using
we have
(ex,  rl,t)( '" i VI).)
== 0
j~e.
(t/I i l/IlIJ == 0,
"'3,
after multiplication with three arbitrary constants Pi and summation win give
3
L {JiAVt,
t= 1
= A
Hence one can always choose three orthogonal linear combinations among
them.
In order to make use of the analogy that exists between the function space
and a ndimensional space to the largest extent, we will consider an arbitrary
function", having components Pl, P2, .... in a coordinate system of orthogonal functions, as in equation (1.21). The scalar product (1/1 At/I) can be
a
(!/I ~ At/!) ==
(1.28)~
L p'taikPk ~
l,l
But if the basis functions are eigenfunctions of the operator A, (1.25) can
be replaced by (1.30) and we obtain
Thus the quadratic form (t/I At/!) is reduced to a "sum of squaresU "
2. It happens very often and particularly if the domain D is infinite t}1~t
in addition to the discontinuous spectrum we have a continuous spectrum
of eigenvalues, and it may even happen that the discontinuous spectrum is
not thereat all. The theory of atoms with a central force field furnishes an
example: the spectrum of energy levels is discontinuous up to a certain limit
(tlie ionization potential) and becomes continuous above this\> Since the
essential character of the orthogonal functions is that they fonD. a denumer
24
VECTOR SPACES 
UNITARY GEOMETRY
[eh. 1, 5
able set, obviously, one does not have the right to apply \v:ithout modification
the language of linear vector spaces 1
The development in Fourier series (1.21) is then replaced at least partially
(compare (1 . 32) below) by integrals. These integrals can be considered as
the limits of series of orthogonal functions.. This permits us at least to a
certain extent to give a sense to the expression of orthogonal functions in the
continuous case. It will be sufficient to give two examples. Let us consider
first functions of a single variable x defined in an arbitrary finite or infinite
domain D and the operator "multiplication by x": (1.30) has now the form
xt/l(x) = exifJ(x),
an equation which has to hold everywhere in the domain D .. It is obviously
impossible to construct an analytical function which satisfies this condition,
but we will imagine a function '" which is everywhere zero except at the
point x = eX and we would consider this as an eigenfunction of the preceding
equation. In order that this has a sense one has, moreover, to demand that
the integral over the product of this function and an arbitrary function
f(x) is not zero. This makes it necessary that the 0/ becomes infinite for
x = tX. We will take this integral equal to f(a):
(J,
f(x)I/I",(x)dx = /(a).
eh. t, 5]
OPERAT()R~
.
.
SInce
one ot,....
trle f unctIons
25
b vD.C' IS
. dff~
zero Whtell tne Gtier
h erent fjrom
zero . So we Inay qualify the sym.bols !/lo..(X) ~~ o(xo:) to a certain extent as
orthogonal and normal function~ depen.ding on a continuous: index Ct" l"'he
"norm" '} hO~Never, is in...'inite as \V{~ can see fron):
if now
Xl
1"
oeCOnlCf:~
11
i)(O}.
The second example will be given \:vitli Fourjer integrahL It \vill be useful
in the next chapter, 'Ve kn.ow that to ext.end the d01TIain uf validity of the
f'ourier series to an arbitrary interval  tZ, +d (0 i.s rcal) it is 5ufficient to
make a change of the variable: t = ,)Lt/a~ In ih.ts \vay we obtain for functions
ljJ defined in this domain, having the periodicity 2a and satisfying certain
continuity conditjons~ the 'veHkno\vn de v elopm.:nts'
~oc
tjJ(x) = (2a)t
Cn
exp (inn:.x:/at
(n
JS
an
integer)~
' I",)"
'
'a
):
(1 rv
""Q} exp ()nnx/
they form a complete set. These are the eigenfunctions of the operator
II
J2ii
Pv L1v
\Ve obtain
== cff~,i n/a.
VEcrOR SPACES 
26
and if a +
00
t/I{x) == (2n)+
f::
UNITARY GEOMETRY
f::
[eb. 1, 5
(1.32)
These are the formulas of Fourier where the index v is a continuous vari
able. The series development is replaced by an integral.
l"he formulas similar to (1.23) and (1.31) are
('" "') =
+oo
00
",",dx
f+oo
00
P:fJ.. dv,
and
~ve
a normalizjng factor that goes to zero if the domain D goes to infinity i.e.
in\ the limit their "amplitude" is zero.
tWe have seen in these two examples the diflculties that will occur if one
d.teDds the idea of eigenfunctions to the case of continuous spectra. It is
therefore better in physical problems to avoid if possible the continuous
spectrum by a limitation of the domain D. The theory of black body radiation
is a wellknown example of this procedure: Conowina Rayleish and Jeans
one supposes the radiation enclosed in a recta.nplar box with perfectly
~waUs. The ampli~de .; of the waves is zero at the boundaries and
therefore may be developed ill a Fourier series and it is not necessary to use
an integral expression.
A similar procedure is used in solid state physics where the Bornvon
~
book~
on
c~~d(:Ultu
(e.g.
WElf,STER,
[1955] p. 153.)
Ch. 1,
S1
OPERATORS
27
~ p" I/It +
(1.33)
a formula that includes as a particular case the series and the integrals of
Fourier.
1
Comparative table of the properties of function space and Ifdimensional vector space
Orthogonal basis vectors
Components of a vector
l
I
_.._
00
~ = S fJi'{;
rx",,, i;xle(
(1.1)
i= 1
'f =
ly=:Ey/e,
1,1
(1.21)
2: YtV~
j L.;ngth
or norm of a vector
023)
{J.3)
(x' y) =
Scalar product
2: >:: y,
(U8)
I
I
,~.,
1_._.:. "'   .
Express,ion for one (;omponent
: :/;!I
Bilinear forms
Hermitlan forms
c'x
)';
17.. ,=
(Uk)
 ;
"'""
.,
2.h (jitX~
.\,t'k
(x . Ay) ~"
O.22~
~~~ t'~(!t;~.J:1f
A{:::xf,t'.)
I
. .  . ~lI
I
I
(ej' x)
Xl
P';'= L (,i!P~,
(I A)
=~ 1: e, 0:, '.
L
'(I'
(1,24)
(1.25)
(ifh.;}.
(1.28)
i,k
(!.ll) I
(If' Alp}
'.~
(A1p' rp),
(1.29)
L=lge:l~t~~~.
C{.Xi
___,_~______!_________
X'
XI
1 ______ _
(1.12,>
a:,~.
<I,k.
('P'A'P)'=2;(Xd3~{J,
(l29a\
(1.30)
(1.31)
'0
p:'"
iO')
VI
CHAPTER
In classical physics wave motion in a continuum is described by the threedimensional wave equation,
(2.1)
A possible elementary solution of this equation is given by
",(x, y, z,
(2.2)
k, == 2ttpv/c;
k z = 2TCYVjC.
(2.3)
The magnitude k is 21t times the number of waves per em; the direction of Ie
is the direction of the wavefront.
Each complete solution of the wave equation (in a box or in infinite ~e)
can be obtained by superposition of elementary solutions. The function
that satisfies (2.1),
00
t/I(x, y, z, t) =
"=00
(2.2a)
30
[eh. 2,
Y,
(2.4)
t=O
The coefficients of (2.2a) and (2.4) are generally complex because the
different spectral components usually have different phases. The relative
phases will determine whether we will have constructive or destructive interference, one of the most striking properties of waves.
The product a: Qt(x, y, z) is the intensity of a particular spectral component Vic of the wave at a certain point x, y, z. On the other hand, if we look for
the average value
of l/I* '" over a time T long compared to the
periods 1/'1k, we have:
<"'. '">
<1/1*1/1>
= lim
! L: fTa:ase2'rl
T+~ T
",J o
(Vrv.)t
dt ...
<"'. "'>
L: a;a,(x. y, z)
(2.5)
,.
Early in the development of quantum mechanics a postulate was introduced that the energy was proportional to a frequency
or
where II
E = hv
(2.6)
E = flO)
(2.7)
== h/2n,
It was successively rea1ized that the nature of the wave was not always
electromagnetic and an additional postulate
(2.8)
Ch. 2,
11
WAVES
31
(2.2b)
two cases.
a) Ifwe have a single wave (2.2b), that is one frequency only, the wave is a
6'monochromatic" wave, the momentum is exactly determined by (2.8) and
the position is completely washed out;
b) How'ever, we do have superpositions like (2.2a) and the possibility
exists to choose the spatial distribution of
t/I*t/I
L a:a e
2xi
(Yk"l)t
k.l
such that "'1/1 is only different from zero in a certain region of space, say at
t == O. If we now interpret the intensity as proportional to the probability to
locate a particle, we obtain in this case a reasonable determiaation for the
position of the particle. This occurred at the expense of a welldetermined
mom~ntum since we must use not one but many differen~ kvalues in our
wave ~ packet.
It}s interesting to notice that the question as to which of the two pictures
is adequate is completely determined by the experiment. This is a special
example of a general pattern iII: quantum mechanics viz. that the choice of
the ~ave function is dictated by the experiment. This choice is called the
state
the system.
If one tries to construct wave packets with the smallest possible spread in
velocity and position, one is led to a Gaussian packet which has tho .property
that the product of the root mean squares of the momentum an<i of the
position obeys Heisenberg's uncertainty principle. Hence (2.2b) or a superposition of similar waves gives a complete and consistent description of the
free particle.
of
32
[eh. 2, 1, 2
can give the formalism an analogy to classical mechanics such that one can
generalize to a nonfree particle, i.e. bound by some potential field, in a
natural way.
.
The function (2.2b) is a solutio~ of an equation of the first order in time.
(but with an imagi~ary coefficient), i.e.:
~ V2 t/!
2m
= h ot/!
i at
(2.9)
L=E
2m
Ii
p~.V.
1
(2.10)
(2. lOa)
= Et/I;
Popt/! = pt/!
Hop'"
(2.11)
(2.lla)
one obtains (2.7) and (2.8). Since the operators are Hermitian, the eigenvalues are always real (comp. Cbapter 1, 5). There arc of course circurp.stances in which the state is not pure (monochromatic), i.e. that a distribution of eigenvalues is found and thus the physical observable is not sharply
determined. The interpretation of such a case will be discussed in S of this
chapter.
2. De Scbriidinger Equation
In this section we discuss the ScbrOdinger equation, i . e. the general wave
equation for conservative mechanical systems, and also we will introduce the
manyparticle equation.
Ch. 2, 2]
33
= 1 p+ V,
?
2m
2.14)
:Ii1 01/1
at 
112
(2. 13a)
(2.17)
THE
nPAl~"rICLE
PROBLEM
34
[Cb. 2, f 2. 3
, t) and V2 is generalized to
2
02
rt+f1:z..
==2
OX t
82
+ ."."2.' ..
(2. 13b)
DX2
Ii 01/1
7  1
at
#1 2 2
Vi t/I+ V(Xl . t)t/I == 0
12m,
L
L,2m,
~ v;.;.r+(E V)t/t = o.
(2.17a)
3. Angular MOJDelltum
3:J. OPERATOR
The only physical quantities that we have studied so far from a quantum
point of view are the energy and the momentum of a particle. They appeared
as operators acting on the wave function.
It
H ==    ,.
i
ot
p~
a
i ax
It
==   ......
It is easy to define in the same way the components of the angular momentum. Let us consider a particle of coordinates x, y, z and momentum
p~, p.,;P. Classically the components of its angular momentum with.
respect to the origin are Lx == YPz:zp,; L, = zpxXP.; L. == xP,YP:._
Provided of course the (pi..wiso continuous) potential function has resioDl in
which it it su1JlcieDtly negative, otherwise the discrete eipnvalues may not occur at aU..
This is Dot the case for harmonic oscillators (compare Chapter' It 5.3.
t
ANGULAR MOMENTUM
Ch. 2, 3]
35
To translate them into quantum language we replace p, and p. by the corresponding operators and obtain
z ~) ,
1 (Y\ ~
ay
vZ
L. = Ii
etc"
(2.18)
Now we can connect the operators and the physical quantities which they
represent with some simple groups or rather with the infinitesimal operations
~'" ==
f o! t5x
'1 OXI
If
iJ
+L==
i
OX,
h b
Of
i 6x
ox
oy
fjz
t/I
==
== 0,
(z ~oy  y~)
';68:4"
iJz
36
[eh. 2, 3
or symbolically
L
n~
= i bOx
(219)
Lx
hL (0
Yi 
="7
1 1
OZi
a\
Zi  )
(2.18a)
OYI
Hence there exists in quantum theory a correspondence between the momentum and the operator which 8enerates the translation group, as well as
between the ~gular momentum and the operator which generates the
rotation group. The equation (2.10)
h a
H=   i ot
shows that the energy is the operator whlch generates real translations in
time. Tbis remArk about the connection between a group and certain operators will be generalized and treated in further detail in Chapter 4, 1c2.
3.3. COMMUTATION RELATIONS
/ L [(y OZa z oy
(1)'(z oxa x oza) =._,,2
== _,,2 L (y!. x~) t/I,
ox oy
(a
a\ (iJ
a)]
z ax x ilz) Y oz z oy '"
~,_e
:
(220)
Ch. 2, 3,. 4r
37
These are the fundamental commutation relations for the operaton which
represent the components of the angular momentum. One can prove by a
similar calculation the commutation relations of Heisenberg.
PxxxPx
It
== :'
P.xy yp~ = o.
(2.20a)
To verifyeq. (1.29) for the Hamiltonian H, one can use (2.14) takinl equation (2.108.)
into ai:Count.
38
[eb. 2, 4
plicative constant; hence they are not really vectors of the function space
but directions or rays. If we wish til t/ld~ to represent a probability we must
suppose that the functions V1 are normalized, i..e.
".
j I{!*t/ldc =
1.
II
State of a system
Physical or observable
~tjty
Wave function tp
Hermitian operator A
acting on 1p
4I~~'III
Observable values of
this quantity
I i.e.
diagonal elemellts
this matrix, which
I
of
has
been put in a diagonal
form by a unitary trans..
formation of the coordi(1.,,,
_________________~f__________________~I_n_at._es__________
IV
I
I
: .  . ._ _ _ _ _ _ _ _ _ _1 _ :_ _ _ _ _ _ _ _
lon
v.. ~oreover we shall allow, following DIRAC [1958], that every Hermitian
operator has a physical meaning!,
lOne can find in the book by VVEYL [1950] (Chapter IV D, section 14) a remarkable
argument that justifies this postulate or at least connects it to a very general and natural
irreducibility postulate.
Ch. 2, 4]
39
It follows from the postulates III and IV that if a system is in the state t/I"
a measurement of the quantity A gives with certainty the value Cl i
VI. But if t/J is not an eigenfunction of the operator A we do not know
with certainty the value of the physical quantity which this operator represents. We can expect to find the different possible values (Xi' CCt with
different probabilities. In order. to make our postulates more precise we
have only to generalize what has been said in 1 of this chapter: '" can be
expanded according to (1.33) in which we shall neglect the continuous
spectrum for simplicity. Then the state appears as the superposition of the
pure states t/I". Each of them is weighted by a coefficient Pic whose modulus is
~ 1 and each corresponds to a given value (%k of the physical quantity A.
JJTe shall assume that a measurement made on the system in the state'" call
: yield any of those values; the probability that this value is (Xi being
fil"
This last postulate foreseen by Einstein, enunciated precisely by Born,
and developed by Dirac can be considered as the keystone of quantum
mechanics . It is the link between experiments and wave theory, giving to
the latter the character of an essentially statistical theory.
If we repeatthe same experiment a great number of times with identical
systems all in the same state t/lwe shall find for the quantity A either the
value (Xi' or <X", or (Xl and the relative frequency of these different results will
be in the limit equal to the corresponding probabilities. The average value of
A in the! state '" is:
P:
(A)
= L CtjPiPt
Lfa.iP:ifJtPi1/!id1:
(2.21)
= L !Pi aUt;
i
The state
L YklPk
k
We have
(1.25)
40
ME(:H.~NICS
[ell.
4, 5
(A) =
III
I. ') 1
(2.22)
lk
(A) is then a quadratic form of the Fourier coefficients Yi. This form w uicb
represents the average of a number of experimental results is necessal"ily real:
it must be Hermitian, since the condition that ail "'Ii YIc+aki ')1t is real implies
III
all == ald
Hence we see the reason why a physical quantity must be represented only
Y:
by an Hermitian operator.
Let us suppose that the state we consider is an eigenstate of the operator
H, for example '" = lpn' 1ft = 1, 'i'lc = 0, k =I: n. From (2.22) one obtains
<A)
= ann.
(2.23;
.j
its expectation value for the state cp" is the element a",. of the main diagonal,
In the foregoing sections the time" t has not been explicitly considere(
since the wave functions which have been used depended only on the coordi
nates~ Now' we shall study the change of the states and the physical obser
vables in time. This will allow us to elaborate the meaning of the equationc
(2.22) and (2.23).
5. TIme Dependence of a State and of a Physical Observable
t/J(x, i)
= L y"Jt)"',,(x),
(2.24
'\,
the coefficients y vary with the time. A conveniellt picture is, the foHo\ving
Ch. 2, 5]
41
the vector tfJ{x, t) of the function space whose length (1.19) is equal to unity
rotates around the origin obeying equation (2. 13a). The problem is to
determine the expression i't(t) of its components along the fixed axes
"',,(x). We have
HI/I
=  ~ at/! =
1 at
~ L I/Ik dl'l
1 A
dt
and since the 1" are ordinary numbers and the t/lt the eigenfunctions of H
we have
HifJ = Ly"H.p" = LYkEkt/l".
k
"
Ii di'k
  = E"l'ki dt
Finally by integration we obtain
(2.2S)
and 
(2.258)
the f1 being constants which may be complex.
'nie 1"'S are always harmonic functions of time with frequency 'Vi ==
27r.4/1J. In a limited sense equation (22Sa) looks like a Fourier expansion.
Particularly if tP is a steady state wave function, this expansion reduces only
to one term (Ct == 1, c, == 0 for 1 #: k) and we find again (2.16). A steady
state is an harmonic oscillation along a Schr6dinger axis, this oscillation
does not give rise to any radiation and therefore cannot be detected by
experiment; since the modulus of the phase factor exp( 27tivJ:t) remains
equal to unity, the system remains on the same ray of the Hilbert space.
If the state is not steady, i.e. if there is more than one non..zero term. in
(2.25a), the motion in Hilbert space will be some complicated rotation.
Let us su~se that the Hilbert space is spumed by another complete set
of ort!to8onal functions tpJ; the transition from the SchrOdinger system tp is
obtaUted by using a unitary transformation U == (uJJ not depending on time.
The inverse transformation corresponds to the operator U1
42
reb. 2, 5
t/I(x, t)
tlJt)
(2.25b)
In the basis qJ, each of the components tfJ(t) of the wave function appears as a
Fourier expansion.
5.2. HEISENBERG REPRESENTATION
(1.25)
We.have been led to this representation because the possible values of a
physical observable (eigenvalues of the corresponding operator) are constants independent of the stat~ of the observed system. But physically the
m~urement of the quantity A is done for a real material system, the siate
of which varies according to the equations (2.24), (2,,25) or (2.25a). The
probabilities of the different eisenvalues at of A and its expectation value
(A) are functions of time.
For example (2.22) and (2.25) give for the Schrodinger axes
(2.26)
43
Ch. 2, 5]
Hence we shall not define the matrix which represents an operator A by its
action on the invariable wave functions t/lk(X), but by its action on the com
(i EJ~E'k t)
(2.27)
which ~differ from the Dirac matrices only by periodic factors of modulus
unity. One can write
(2.26a)
On the other band, (2.27) gives
h dL4Jt
i dt
EJE" AJi:
(2.27a)
:=
= U1EU;
(qJt) == U 1AU ==
(L uji1AJmu,.).
1m
The coefficients qJIt. are complicated functions of the time since the sum. LIM
is a series expansion which involves all the frequencies (Oil; equation (2.27a)
becomes:
It ~ == h U 1 ~ U _ U1(EAAE)U
i dt
i
d,
== u 1 euU 1 AUU 1 AUU 1 EU
44
[eb. 2, I S
or
AdQ
:= HQQH
(2.28)
i dt
the wellknown equation of Born, Heisenberg, and Jordan 1 We shall

in
1 This equation which is lO~es called the equation of motion of matrix mechanics
leads to a direct connection between quantum and classical mechanics. Classical equations
such as Newtons law, the virial theorem, and the Lorentz force can be mimicked by UBiD,
matrix notation. (Compare SCHIPP [1949} Chapter VI or DIRAC {1958] Chapter Vl.)
Ch. 2, S, 6]
45
TRANSITION PROBABILITIES
In order that an experimental intervention of the observer can be considered as a sudden intervention it is necessary that the rate of spontaneous change
of the system be small with respect to the rate at which the external perturbation is established.
A very simple case is when ,one considers the eigenstates "',. of the Hamil.
tonian operator H: all the coefficients in the expansion (2.2Sa) are zero
except en the modulus of which is equal to unity. The equation (2.26) shows
that (A) = ana is independent of the time t and can be considered as a time
average of the quantity A for a system in the state "',.~ Let us clarify the
meaning of this statement: If a series of measurements of an arbitrary
quantity A is performed for different syste~s of the same kind and in ,the
same state t/I,. their average does not depend on the instant at ~lhich each
measurement is done. This is the reMon, why the states corresponding to the
level En are said to be stationary states.
In the old quantum theory the meaning of the expression Htime average"
was rather intuitive. It is not.possible to indicate such a thing for a quantity
represented by a nondiaioiiai matrix.
One ~ust note ttiat the stationary states of the atomic systems with which
the qWmtum theory is principally concerned are onlyapproximalely'stationary, provided "the ~tion dampingu is neglected (compare the next
section). As. the frequency increases this . damping becomes more and more
imp~rta.nt, it accelerates more and more the rate of the sponta.t1eous' evolution br the systems, it decreases their u mean life' which can be less than the
duration of an observation.
"
,~
:,,",
,_
~~
~. ~
,,<
,i,
e'
The original basis of the present quan:tUtntheoty is the Bohr postulate, i.e.
an 'atom raoi8.tes when it changes from an en~rgy level E. to a.lower en.ergy
level En; during this transition it emits a quantum ofelecttomagnetic energy
flO)
= W
II::
E".  E. .
(2.29)
46
[Ch. 2, 6
fA,,(t) ==
(2.30)
p."'. == :E t/I"Pb
(2.31)
Ie

(I/t", iD/I.) ==
J"': ~
I/t"Pud'C  ",.
(2.32)
When m and n,arc both large and when their difference is small,.,the formula
I
Ch. 2, 6, 7]
47
PERTURBATION THEORY
(2.30) must be valid. This use of the correspondence principle leads to the
following result, which can be obtained rigorously using timedependent
perturbation theory (the socalled "Goldenrule"). The energy radiated per
second is equal to the average number of the transitions, i.e. to the probabili. .
ty of transition P mrt multiplied by the value of the emitted quantum. Then
one gets
1 dW)
P1ft,.:: (  hv dt
4n {2nv)3
quantal1y translated as P mn = 3
3 he
Illmal.2
(2.33)
It was later shown by Dirac, that a similar formula is valid for spontaneous emission, i.e. when the atom is not subject to an external radiation field.
The preceding result is the basis for the selection rules: if
~==p~==p:'=O
The numDer of problems in quantum mechanics that can be solved explicitly is rather limited, a situation similar to classical mechanics, or statistical
lI,lechanics. To study more complex questions one must often be satisfied
With successive approximations starting from the cases for which solutions
are known.
This method, is called the perturbation method: the energy levels E 1 , E 2 ,
and the complete set of eigenfunctions
of a given Hamiltonian
are supposed to be known. They correspond to the Schrodinger equation
HIjI,
= Ett/l,.
(2.34)
The aim is to calculate the energy levels E' and the eigenfunctions "" of the
system disturbed by a perturbing energy which is added to the Hamiltonian H
and which is generally supposed to be expanded in a power series of the
paraineter A.. Taking into account the terms of only first order, one gets
H' == H+)'W
and (2.34) becomes
(H+AW)1/I' = E'1/I'.
(2.35)
48
reh.
2.
One can proceed with this approximation to any order. The formal calculations remain simple, but the practical difficulties become quicldy inextricable. Particularly it often happens that the series which are thus
obtained are divergent. We will discuss here neither this kind of difficulty
nor the case in which the spectrum of eigenvalues is partially continuous.
7.2. NONDEGBNERATE PROBLEMS
Let us suppose that all the levels E, of the unperturbed equation (2.34) are
single. The eigenvalues E{ and eigenfunctions t/I; of the perturbed problem
(2.35) are slightly different from the energy levels E, and. the eigenfunctions
'" ,. Therefore we can put
(2.36)
E; = E,+AWi
l/J~ ==
and we expand
Ui
1/1,+ AU,
(2.37)
"t == L e""".
t/!,.
(2.38)
Using Jhose three expressions in (2.35), taking into account (2.34), and
neglecting A. 2., we get
W.p,+
(2.35a)
1/1,.
(2.39)
system
~,.]
LI \lI,(wu w,e5,,Q,,(B,E,)] == 0
o
{
~n == 1
(2.3Sb)
(i#:l)
(i == I)
and as the basis vectors '" J are orthogonal, the brackets are all zero.
Then, (a) for i ~ I
(2.40)
(b) for i
=1
(2.41)
Ch. 2, 7]
PERTURBATION THEORY
49
and one can suppose Cu = 0 (in such a way that the norm of t/I; is 1).
The problem is completely solved in the first order and we have to calculate
the matrix (Wit) which according to (2.39) is given by the expressions
f "'~W""dr: == w"
(2.42)
(2.43)
allows a different eigenfunctions 1/I,(i == 1, 2, ... (X) which mayor may not
be orthogonal. These eigenfunctions are determined only up to an arbItrary
unitafy transformation. One can build a: independent orthogonal linear
combinations with these eigenfunctions which also obey (2.34a). As previously, we assume that we know tIle complete set of eigenfunctions t/J of the
operator H which contains the ex functions
Generally the perturbation splits the energy level E into (l different levels,
close to the unperturbed level
"'f.
E; = E+AW,.
E;
(2.36a)
tI
"'; =
11
11k
t/lk'
I = 1 ... lX.
50
[Ch. 2, 7J
1,,,.
ex
ex
"'; = k=l
L 'P,Ie 1/1" + AU, =k=l
L 1Uc I/Ik +1 L, Cil t/t~
(2.44a)
it k = 1, 2, ... (X
== (X+ 1, +2 ...
where the zeroth order coefficients "la, and the first order coefficients e,l
(H+1W)t/I~ ==
or
ta~g
(E+A,w,)t/li
CX>
L
cu(EE,)J/i, = L 'YUc(WI/I1c Wit/!t)
1=+1
k=l
(2.45)
As in the first case let us expand W",,, in a series of functions t/I" but
writing separately the Cl first eigenfunctions t/lJ' equation (2.39) becomes
<Xl
Wt/I" == Jl
L '"J Wjk + ,.+
2: 1 .p. V,,,
where
Va
(2.39a)
(~a)
Q')
L (1UcWJIt;'YIJWf)"'j+~EvyUt.Vl1c"".
il;
i,j1
(2.4Sa)
Ch. 2, il
PERTURBATION THEORY
51
zeros in order to change them into matrices which are defined for all the
values of the indices from 1 to 00. This allows us to put (2.4Sa) into the
following condensed form
co
1=1
(2.4Sb)
The brackets are zero since the t/J I are orthogonal. The equations which are
obtained this way can be classified in two groups:
(i) I ~ cx, El = E, vlk == 0 and (2.45b) yields
2: 11k WIt 
i'll Wi
where the
=0
( i, 1 = 1, 2, . . . <X)
(2.46)
w,,, are known coefficients (cr. (2.42) and later (2.48). This system
Wll WI
W12
W21
W22 Wi
Wl
I
~~: I == 0
Wt
w....
(2.47)
wll
whose tX roots: Wl, W2, W4 are real, since the matrix (WII) isHermi~
(as will:.be proved below). To each root wJthere corresp()Jlfis3 system ,of
coefficients "Ij!,  1jfl. which are determined by ~ homogeneous equations
(2.46) except for a multiplicative constant. One takes this opportunity to
normalize the eigenfunctions .pi If the secular equation has multiple roots
the degeneracy is not completely removed and some Yilt remain undetermined.
The practical difficulties are purely analytical. One must calculate first
the elements Wu; of the perturbation matrix: according to (2. 39a). These
elements are given by the integrals
Wu.
f",:Wl/lk d
7:,
I S.o%
(2.48)
52
[eb. 2, 1
the evaluation of which is generally difficult. One then has, to solve the
algebraic equation (2.47).
(il) Now let us suppose 1 > cx, W,,, = 1'u = o. According to (2.45b)
we have
ex
 ~ Yii, V,le
CU  L
(2.49)
== roll ,
i  I EE,
EE,
with (cf. (2. 39a))
= "'~W",,,d"C.
Vrt
0)1l
I'ik V,,, =
1 > ex
f "'~W"'fd'C.
(2.48a)
Let us suppose that all the levels are distinct and that two of them El and
El ar~ closet. Let us write
(2.49)
E2 ; El being fixed by the nature of the unperturbed system, the auxiliary
~eter" is very large when the perturbation ;"W is negligible, and is of
the _o~der of unity when this perturbation becomes of the same order as the
difference E2  E 1 In this last case the perturbing action will almost
couple those two levels as if they were degenerate. As in (2.44) one is led
to put
co
l/I~ ==
I'll
'3
"'; =:
00
"'3 + l L
)=1
(2.44a)
e3l"'J
(~h.
2, 7]
PERTURB.~TION
53
THEORY
level E = E1 and in order that the eigenvalues Wi are 0 and '1 in the absence
of the perturbation, we replace Wi by Wi 11 in the lower righthand corner of
the secular matrix. The equations (2.46) which determine the coefficients
Yik can be written
J'il(Wl1 W i)+
'Yi2W12
+Yi2(W22 +l1 W
1'il W 21
O}
=
= 0
= 1,2
(2.50)
=0
the two roots
WI
and
W2
(2.51)
are given by
w = t[W11 +W22+'1+~(W22+11Wl1)2+4w12lV21].
(2.51a)
We have finally
E;
~
1'22 ~
I'll
E~ = 1 +A.W11
== El + A(I'J + W22)
= E z + AlV22
Y12
1
1
~ 1'21 ~
(2.52)
o.
We will first discuss the special case in which both WI2 and W21 happen to
be zero. '[he equations (2.52) ~emain valid no matter what the order of
magnitude is for'1 and equations (4~51) reduce to a system of two equations
of the first degree. No c0'!Jpling between the two close levels is established,
and when the perturbation becomes stronger the two curves E:' == E{(A),
E~ = E~(A) cross without mutual modification. Their intersection is at the
point w~ere
W1t
(It
i~
necessary that
=:
11+ w 22
WIt  rV22
I.e"
A=
E2El

W 1 1  W Z2
54
[eh. 2,. 7
On the contrary if Wl1 :p 0 this intersection cannot occur. The two roots
are always distinct since the radical involves the sum of two squares. The
two energy curves come closer, the energy difference becomes a minimum
r
which is equal to 2v'W12}V21 when A = (E2E1)/("Vl1W22)" and then
the two curves diverge.
It is also interesting to examine the behavior of the wave functions
during this process. It is now a simple matter to calculate the coefficients
7. We find:
yil == li2 = t[1+(W 11  W22,,)/D]
112
== yil
:=
where D is the (positive) square root in equation (2.51a). For large positive
" : )'11 == 122 == 1 and 121 = 712 == O. If we let El and E2 "cross over", "
changes sign and the result is that for large negative" we have 111 == 121 = 0
and 712 == 121 = 1. Hence if the system was originally in the state E 1 , the
lower state, it will now be in the lower state (E2 ) again. This is only true if
W12 p: oand as we saw above the energy levels do not actually cross over but
do ooly approach each other closely. During'the closing in, the wave functions get mixed and after separation turn out to be interchanged.
The preceding considerations can be applied to the theory of complex
atomS, where the perturbing function represents the mutual interaction
of
ionized 1~
A similar case occurs when one of the atoms has an excited level near the
Nevertheless the bond remains homopolar (Fig. 2. 1) but the number 1,,"1" gives, as a
function of R, the percoatage of ionic state contained ill the 4i.Ctual state :pi and consequently its contribution to the electric mOlnent of tI\e moi~ule in the ground state.
1
Ch. 2, 17]
5S
PERTURBATION THEOR.Y
__
E~
~~
.. R
R'
Fig. 2.1. Two enClIY curves as a function of the parameter R. OJfdialonal elements are
zero at the point of intersection.
't
When n electrons caD be ponnuted tho c:lepDeracy is of order II! One mows
the
electrons which are permutecl can be connected to the same Ducleus but in cWrerent .~tes.
1
56
1/11
[eb. 2, 7
is symmetrical,
"'2
(tonie)
(Homopotar)
E.
,..R
R'
Fig. 2.2. Illustration of the noncrossing rule: Offdiagonal elements are nonzero. Notice
the labeDing of tho curves.
Ch. 2, 7]
PERTURBAtiON THEORY
57
definition (2.39a) of the matrix WIlJ one can easily perform a first order
calculation, following the calculation done in 7,,3 of this section. The
further approximations are more difficult.
Let us make a last remark: we have the study of nondegenerate, degenerate and quasidegenerate problems divided in three parts, 7.2, 7.3 and 7.4,
but the method which is used to solve these problems is always the same, the
last case is the bridge between the two others.
GROUP THEORY
t.
Ch. 3, 1, 21
EXAMPLES
S9
_onsaeeable.ftom
1. Examples
2.1. GENERAL CONSIDBRATIONS
1 2 3 .. ")
PI
== ( 3 7 6 .. k
60
GROUP THEORY
[Ch. 3, 2
1 2 3 ... )
4 9 . ... ..
= P2 P 1 = ( 5
We say that s is the product of the two permutations PI and P2' using
the convention that the first operation will be written at the righthand side.
This will permit us (if necessary) to place a symbol representing the collection
of objects on which they operate at the rightl. This rule is general. that is
we will use it for arbitrary operators acting on different mathematical
objects: vettors, functions, etc.
Among the permutations defined in this way, there is one that does not
change the place of the objects. This is the identity, B, which obviously satisfies the relatioDs:
EP
PE
= P;
_(11 22 ....
.... n)
E
..
Ch. 3, 2]
61
EXAMPLES
and its image point pi, thus we have effected a transformation A of the
onto itself. We will express this by the notation
P + pi
== AP.
p + P"
s~ce
== cP
.+,
P"
= BP' results
= BAP,
EA
==
AB
==
A.
62
m.
IV.
[Ch. 3, 2
GROUP THEORY
==
AA 1
A 1,
called the
B.
(3.2)
(3.3)
gen~
do
A+O == O+A ==
A,
m.
the inverse of A is  A.
This group is Abelian. It is an additive group of infinite order.
+"
63
EXAMPLES
Ch. 3, 2]
itself, one of the few in which tPe operations do commute. Affine geometry,
i.e., the me,tric used in vector spaces, is the study of the group just mentioned
't!ith one 'additional property: each operator or vector II may be multiplied
with a real number if we deal with a real space~ or with a complex number jf
we deal with a complex or unitary space. This is called "" additive group
with multiplicators. The mapping of a vector space upon itself results from
the combination of two processes, the process of addition and the process of
multiplication by numbers. These numbers are operators acting on the
vecton. These vectors are themselves elements of an additive group. The
operators could be of a more general form than simple multiplicators;
for instance matrices. Hence a vectorspace, on which a system of matrices
acts can be considered as an additive group submitted to a 8Ystem ojoperfltors.
The extension of the theorems for the theory of groups to this particular
case is of tremendous value.
2.4. GROUP TABLE
In summary, a
group consists of a set of symbols satisfying the post1i(ate8
"'u
I and IV for w1Jich the "multiplICation rules are given a priori. These symbols.
,
represent operations which are not specified by the abstract .grouP. theory.
An abstract aroup outlines the properties of a certaitl numbe( of concrete
groups~ which are realizatio1J3 of the abstract group, in a kind of Pythagorean ta~Ie (CAYLEY [1854]), usually called group table. For example: Each
otthe t~o Tables 3.1 and 3.2 represents an abstract group whose properties
are those of the group .9'3 of permutations of three objects and those of the
groul>~ of operations which brin, the equilateral triangle into coincidence
witb1tself including the possibility of turning it over on its face. We can give
the following significance to the symbols in the table: A is a cyclic permutation
(~ ~ ~) or a rotation of in ~ound an axis normal to the center of the triangle;
B := ~2 is the inve~~ of the previous permutation or rotation of
around
the same axes (~ : ;); c, D, F thC transposition of two objects or rotatioJ1S
around the medians of the triangle [Compare Fig. 3.3]. '
Table 3.1 looks like an ordiDary multiplication table. In Table 3.2 the
sequence of operations in the first column is not in the order E, A, B, C, D, F,
butinthoorderoftheirinversesE,A 1 = B,B 1 == A, c 1 = C,D 1 == D,
J
tn
F1
J
==
p.1
A.
= AC
64
[eb. 3, 2, 3
GR.OUP THEORY
TABLE
3.1
TABLE
EABCDF
EABCDF
E
A
B
C
D
P
EABCDP
ABBDPC
BBAPCD
CPDBBA
DCPABB
PDCBAB
3.2
EABeDJI
AI = B
B1
A
DEAFeD
ABBDF'C
CFDBBA
DCPABB
c
D1
F1
==
=
::=
C
D
F
PDCBAE
3. Subgroups
3.1. DEP1NITION
It
/I
ut3.
Ch. 3, 3]
SUBGROUPS
65
66
OROUP THEORY
[Ch. 3. 3" 4
= Ih.
(3.5)
==
... J't's,.
. (3.4a)
The nature of the cosets does not depend on the choice of the generating
elements ~, S3 They are uniquely determined by the structure of "
and rt>. To sho~ this proposition let us co~der an arbitrary element
82 of 828. We claim. that .S2.1t' :; S2J't'. As a mauer of fact s; can be
written as t2D uit bcJonp to. S21, where D is a ~~ elemeD~ ~r Jr.
Hence sil consists of the collection of elements.f2DA, SJDBt S2DP, i.e.
those of S21 written in a different order (compue 1).
In the examPlo of 2.4 the subgroup .ttI3 (A, B, B) possesses a single coset
~3 = Dds
P~3 .
The ume eonsideratioDs
. apply for infinite groups. The index I of I could
then be finite or infinite.
Let St, for example, be the set of vectors in a threedimensional space,
considored as an additive group, I the Bet of vectors _ of the xOyplane
andr~' a, 'lCdornot located in 4f'. Then ,4f' is the set of all the vectors , + "
taU.the points S' are in a plane Z parallel to xOy. Each of these
planescetfllPond to, a coset associated with 4f'. ~ere are a continuous
bJIlaite number of these planes (compare Fig. 3.1). (Sec p. 69.)
'
~
fro. ..
i
Let
Y:r::AX.
(1.4b)
s,'
: We can consider this from two points of view: either the axes stay' fixed
and we let a transformed vector y = Ax correspond to the vector x (A
Ch. 3, 4]
67
represents a mapping of the space upon itself), or the vectors % and y are
identical in space and the axes are rotated. If (1.4) is considered as a change
in basis vectors we find according to (1.3a) that the basis vectors underwent
the transformation A 1.
Let us take now two transformations A and S and
(3.6)
then by using the first interpretation, i.e. the axes e, are kept fixed, we ~y
that the matrix 8 produces a mapping of the space upon itself; which in
general differs from A: we say that the two transformatio1l3 A and 8 are
conjugated.
With the similarity transformation (1.7), or the second interpretation
used for the Illatrix S, we know that they go over into each other by a change
of coordinates S. Hence two conjugated linear transformations are in general
different but equivalent in the sense that either one can be obtained from the
other by a transformation of axes.
4.2. GENERALIZATIONS. INVARlANT SUBGROUPS
Two elements A and B of a group ~ are conjugated if one can find a third
element s of the same group, such that
(3.6a)
==
AS
or SAS 1
68
GROUP THEORY
[Ch. 3, 4
(3.4)
We claim. that each term of this sum may be considered in its turn as an
element of a new subgroup, called the factor group of 9J and designated by
the symbol t/.Yl'.
Indeed if we take the product Si .Yl'Sj:/l' we obtain a coset containing all of
the elements of t which are of the form 8, ASJD, A and B belonging to:/l'.
We claim. that this product: is one of the cosets associated with :/I' in (3.4),
that it is the one which contains the element St =:II S,81 and which we designate
by s".Yl'.
Indeed
S,ASJB
==
1
s'SJSJ ASJD,
= SiSJC ==
S"C ..
If we take for A and B all other elements in .Yl', keeping s" fixed, c will vary
but remain in :/t' and hence we will have
(3.7)
i
we
'1
'2 =
If
put
=:/1',
The left and right cosets are the Same in tho case of an invariant
subgroup~,
as
Ch. 3. 4)
CONJUGATED ELEMENTSCLASSES
69
If AS ==
SA
~~~~~~~~~~~~~~~7
,/
,/
/'
/
/'
/
2//
/.
/'
" 'st
/' /
'"
;'
== xay.
difference lying in the plane 1l2 In the same way we treat angles intrigonometry where 45 and 405 are considered identical disregarding the difference
of 360. The latter is irrelevant in certain cases as for instance the calculation
of the trigonometric functions.
The figure accompanying the previous formula is identical with (3.1).
The plane Z is the space Bt2 ; all vectors v, 1", 1''' etc. are vectors between the
origin and a certain point in. Z.
70
GROUP THEORY
[eh. 3, 4, S
v ==
~
v~,
==
1)~'
(mod
J
Yt')
s.
or n
Objects :7,.
= (1 2 3 4 5).
the permutation can be separated into two cycles, each set of elements forms
an independent cycle that tenninates in itself. An object that does Dot move
fro~ its place will form a cycle on itself. In this notation one encloses it
between brackets or sometimes one omits it altogether. The order of a cycle
is tlie number of objects contained in it .
,Only three things are important in this notation: the number of cycles,
the objects contained in each of them, and the succession or order in which
they appear in the cycle. One can arbitrarily choose the order of cycles:
(1 5 3) (2 4) = (2 4) (1 5 3) or the object that appears first in a cycle (1 5 3) :;::
(5 3 1) = (3 1 5).
A transposition is a permutation of two objects. The following permutation
is equivalent to a single transposition:
f
G~ ~ ~~) = (2 4)(1)(3)(5)
(24).
or
(2 4)(5 3)(1 3)
Ch. 3, 5]
71
GROUP OF PERMUTATIONS
but in the cycle notation we usually arrange the objects such that the diffetem
cycles do not have an object in common. A permutation is even, or odd nit is
the result of an even or odd number of transpositions. This is called the
parity of a given permlltation.
One can show  and it is almost obvious  that the parity of a pennu~..
tion is unambiguous, i.e. independent of the manner in which one decomposes it into transpositions.
The inverse permutations of a given permutation can be obtained, in the
cycle notation, by reversing the order of the terms in each bracket. The
order of the brackets as a whole is irrelevant since they are independent.
(1 5 3)(24)1 = (3 5 1)(42)
= (1 3 5)(24).
If we have
n)
s = ( 1. .2 ... . ;
J1 12
'II
1 2 ~ .. n )
( k 1 k2 . kll =
(i11 i212 .
ill)
. I,.. ;
1
then,the conjugate of s with respect to Tis s' = TST 1 , where we have to read
the operations from the right to the l~ft, so we obtain
I
 1
S=TST
k
z
ka)
.
11 11, " I,.
\' k 1
we have to carry
out the permutation T on both lines of s. This rule can be transferred ..uy
to the cycle notation: suppose the s requires several cycles~ It is then obwOJlSly sufficient to carry out the permutation" Ton the terms. ofeach,cyclc.:in
order to obtain TST 1, i.e. we neither move the parenthesis nor chan.~the
number of cycles, nor the order in which they appear. Take for example,
s = (1 5 3)(24), T = (123 4 5)," then, formingthe conjugate, wohaveTST. 1 ==
(2 1 4)(3 5)~ In brief, to go from a permutation to its conjugate mtaDl:to
change the labels of the objects which one permutes without mOttifyiDgtb.e
manner in which they are permuted.
From this we see that a claSs ofpermutations (compare ,4~2lis.complllely
determined by the number of cycles and the order of each of them.
T,
72
GROUP THEORY
[eb. 3, " 6
This is the group formed by all the even :Permutations of " objects, a
subgroup of index 2 of /,.. Its coset is a set of odd permutations;
these permutations do Dot form a subgroup since the product of two odd
permutations is oven. d"js an invariant group of !/,., according to the rule
of 5.2.
Most of the preceding results were obtained by Cauchy.
6.
isomorphism ad
HoJllOlllOl.Pldsm
6.1. DEPINITION
.t
,Let us suppose that the correspondence between tJI and fI' is not onetoone,
means that to an element A' of ti' there will correspond several
dUlerent elements At, A2' A, of 16. Any element A of <6, for example A"
multiplied by one of the elements of (I corresponding to B' in '6' should
lead to an element Ci which corresponds to A'B' = c'. (see Fig. 3.2). In
this case, the gI'Oups are called homomorphic, that is the isomerism is
merohedral
These concepts are used in crystallography and 'one can find a number of
examples there. A simple arithmetic example is the following. Let V,. be
the grOUP of permutations of n objects. With the even permutations we
ass~ociate .the number + 1 and to the odd permutation the number 1.
The multiplicative group tN' consists of two elements + 1 and 1 and is
homomorphic to f/". The element + 1 corresponds to the alternating sub
73
Ch. 3, 6]
is homomorphic to the factor group t6/~. All the elements of ~ correspond to the unit element P1 of t6/:JIt' and those of the complex s.~ to F,.
The converse of this obvious statement is also true and forms a fundamental
theorem.
.'.'.c'
At
,.
"at .
l'
_..... ........
..,
At
/1\\
belo", to
//I~
;/,~
All
_, 8j .........'"
C:,
.. ........ ....
A/ .) 
c;.
e..... e,l

betongto1
sro~pa.
TheOr.m: lft is homomorphic to ~' and letting ,H' be the unit element o/tl
l
,
then:
==
X'X,l
= E'
74
GROUP THEORY
[Ch. 3, 6
REDUCIBILITY OF
Ch. 3, 7]
REPRESEJ:"rI'!\T!O\I~S
75
7 Reducibility of RepresentatiG113
7~1.
INVARIANT SUBSPACE
X m +l =
X'II
A= (Poa SaQa)
(3.8)
76
GROUP THEORY
[eb. 3, 7
projecting the vectors of tJl parallel to il 1 , i.e. by projecting all those that
differ only by their nl first components into one single vector. We will designate these by the symbol 0l/Di 1
.
Indeed, if we consider the vector space at as an additive group with operators defined by the matrices of the system '#, Uti is an invariant subgroup
\vith the same operators (invariant in the double sense of the word with
respect to tlle transformations of t and also because the group is Abelian).
miDlt is the factor space as defined in 4~4 of this Chapter. IIencef the
matrices Sa form a representation of (I itt the factor subspace 8l/Dl 1 7.2. COMPLETE REDUCTION OR DECOMPOSITION
The most interesting cases are those in whlch one succeeds, by a. conven. .
ient choice of axes, to decompose the space
into two independent in~
variant subspaces Ul1 and tIl 2 All the rectangular matrices Q. become zero
il~nd the matrices of the systenl 9J take on the fonn of So step""~JI~fe matrLy~
Po
(o
0\
~'SI1) ~
'Inus the representation, or more generally the system of matrices II decomposes into two representations or into two separate matrix systems, one with
m, ihe qther wit.h It  m dimensions.. Tras is called a complete reduction or
decom1'1d,Sition . This is indicated by a S},mbolic plus sign:
i
'11+~2'
(3.9)
9l = fRl + tllz
(3 ..9a)
!f
e.s
hence Ut1 is isomorphic with Ut/Dt1 Thtoreffi! Every systllm of reducible Ul'iitar,v matrices is decompoaabky, i.e.
for a unitary system we can always go from (3.8) to (3.8a) by a suitable
ehanae of coordinates..
It is sutB.oient to take in the unitary space It  in which the tranaformations of the system tI are performed  a set of axes such that the first m
span the space 1 and the remaining n  m span a space 812 that is orthogonal
to til' i~Oo~a space that contains all the vectors "perpendicular" to at t Since the transformations !I are unitary they conserve the orthogonality
relations among vectors. They transform. III into Jtself and will do the same
to ~ as this space is orthogonal to Ill The result is that the second one is
in,variant too.
Ch. 3, 71
7'7f
REDUCIBILITY OF REPRESBNT..J\TIONS
An isolated unitary matrix can always be brought into the diagonal form.
For a system of unitary matrices this is only possible if these matrices
commute with each other (compare 3.3). rHe assume of course that all tllC
matrices of the system are transformed with the help of the stIrne transformation matrix.) If the matrices are not commuting, we can only hope for
the simultaneous reduction of aU the matrices of the system to Hboxes n
of the size ml, m2, .... m,,(ml +ml + .... mil == n) along the diagonaL If this
reduction is carried out as far as possible we say that the system of matrices
is reduced and the parts, each corresponding to one set of boxes (one for
each matrix element of tf), are called irreducible .
""hen we qeai with the representation ~ of an abstract group ~~ it
important to decompose this representation into irre,/u[:ible representatioru;
since, as we will see below, only these have a fundarnental ll1eaning in physies
and mathematics. Once we have found these ].1 irreducible; constituents ~ 1 ;
t#2 . ~ . t6 p we can again use the notation introduced ir: equation (3~9)"
~ = tfl+~2+.
4.
J)~
tlnite~
EXAMPLE
We will again use the group [/3 since this is the simplest example of a
non=Abelian group. The elements are the six permutations (1), (1 2), (2 3),
(3 1), (1 23) and (1 3 2). In order to make use of the group table in 2~4,
Chapter 3 we indicate the isomorphism: (1 23) == A; (3 21) == B; (I 2) = n;
(2 3) 5: C and (1 3) := :F.
It is easy to find a representation of this group., Let us take for tbeobjects
which permuted the three variables Xl, Xl and X3, i.e. the three projections
of a vector % on three rectangular axes 1, 62 and ',. The different elements
of this group are represented by the system of mapping equations:
(1 2)
+
Yt ==
Y2 =
13
X2
Xl
e: X3
(1 2 3)
+
Yl
==
Xl
Y2
=:
x]
Y3 ==
Xl
etc~
78
tCh. 3, 7
GROUP THEORY
010\
(1 2) ~ { 100)
\001/
010\
(1 2 3)
+
( 0 0 1)
\100,
etc.
e;
e;
e;
Fig. 3.3. An object that allows tho six operations of the group .9', Indicated are the threefold axis (perpendicular to the plane) and the three twofold axes (in the plane).
t.f .t~ke.
.<~t
"
Ch. 3,
71
REDIJCIBILITY OF REPRESENTATIONS
79
1\
Fig. 3.4. l'he choice of unit vectors that establishes a decomposition of the representation
into two irreducible representations.
..
GROUP THEORY
80
3~
[Ch.
.93 == d,+(12)J7I'3.
(1 2)J:l3 is the coset associated with d, and consists of the odd permutations (1 2), (2 3) and (3 1). If we let the number 1 correspond to the
elements of the coset and ifwc let the number + 1 correspond to the elements
of the subgroup, we obtain the antisymmetric representation of 9'3 The
identical representation could be called the symmetric representation.
As a matter of fact any symmetry group f/ ft must have these two representa...
tions as is obvious from the explanation in 6.2. It is possible to prove that
for !/3 only these three irreducible representations exist. As a last remark
only the twodimensional representation is faithful (c.ompare problem 391) .
It
7~S.
FINITE GROUPS
x:
Ch. 3,
81
UNIQUENESS THEOREM
81
;t
WII and
we must have p :: pi and the two sequences are formed by irreducible representations which are one by one equivalent after changing the order in a
proper way.
In modem algebra which deals only indirectly with the notion of representations this proposition is connected to a more abstract theorem due to Jordan,
Hoelder, and Noether.l
In order to give an idea of the proof of the theorem without goinS into
details we will show it for c)nly three dimensions. "fhis gives the possibility of
specifying the precise meaning of the process of decomposition with the
help of a simple geometric example. In the case of a threedimensional space
two hypotheses are possible, either the irreducible invariant subspaces are a
plane 81 2 == .%Oy and a line Btl == Oz" (If the representation is unitary the
line is perpendicular to the plane) or they are Li.e three axes til := Oz,
9l~ :; Ox and tI~! == 0)1"
1. Suppose the first assumption is true:
81 3 = al1 +2
i.e. e~h vector of Ita that iOC$ through the origin can be decomposed unambigUously into a. component lying in III and a component in 8f.l and eB.ch
of t~se will stay in its subspace under the transformations of the representati0ns 'I of the "group '6. It is impossible to find an invariant ,plane Iii
that does not coincide with fIl 2 Indeed if'it existe~ it would cut 812 along a
line L. This line would be a.n invaria.nt subspace of 812 since it is the intersection betWeen two invariant subspa.ces. But III is irreducible, tho tine L
cannot exist and each invariant plane Iti has to coincide with 8ll o In the
same way it is impossible to find an invariant line Iti outside the axes
Oz == tll1 because if it existed it would determine with this axis an invariant
SPBlSD.
82
GROUP THEORY
[Ch. 3jO
8~
9'
y = Tx.
(3.10)
Ch~
3, 9]
83
SCHUR'S LEMMt\.
vectors in e which are not used at all in our homomorphism, that is they do
not" correspond to any vector of R. 1
Having supposed all this we assume:
1. that the system r#R is irreducible;
2. that the matrix T establishes between the vectors AR% and AsY,
BRx and BsY, etc.... the same correspondence as between x and 1, i.e.
AsY
= TAR.%';
BsY
= TBRx;
(3.10a)
or, by taking into aCCGunt (3.10) and leaving out the vector symbol x
As T =
TAR;
BsT = TBl{;
(3.11)
. . .
From these two hypotheses we will show the fonowing theorems (compare
Fig. 3.5).
Fig. 3.5. Sylbbolic representation of the assumptions on Schur. Lemma. Spaces It and e
are represented by point sets.. The mapping T by connecting lines. e' is that part of S
actually used in the mapping T. Since TXt) is equal to zero, then Tx a , Txv, etc. are also
equal to zero. We prove that either . ' = 0 or Bl' = 9t
Theorem ~I. The relation T existing between 81 and ~ is either an isomorphism and Det T =F 0, or T is identically zero. Indeed if we consider the
subspace Dl' of Ul that corresponds to the nullvector of and we let %0
be an arbitrary vector of this space then by hypothesis we have y = T Xo = 0 .
tllXl+tlJXt+tlaxa;
)" = tUXl +tasXs+/aaXa,
establish a relation sut;h that to ~ch vector It of a threedimensional space 1t8 there corresponds a vector, y~t the plane y10y, in the space e and if tbis space has more than two
dimensions, its vectors lying outside this plane do not correspond to any vector ina"
The vectors in It that correspond to the nullvector in e are those which lie on a line
whose equations are determined by,puttina the lefthand sides of the preceding equations
, equal to zero. To a given vector y =1= 0 there corresponds a set of ve;ctors in 91. !1aving their
origins at 0 and their end points on a line parallel to the line lnentioned above4
Yl
(Ch. 3, 9
GROUP THEORY
84
The matrix T makes the vectors AR%o, B.. %o, correspond to AsIa,
B s 10' , according to (3. lOa). Because Yo == 0 the latter are all zero.
Hence A.. %o; Ba.o; all belong to the subspace at' which appears to be
invariant with respect to the transformation of the, system ' ... But we have
supposed that this system is irreducible and we are left with the following
alternative: either It' = It, and T%0 == 0 for every %0' ie. T sa 0; or al' == 0
and the nullvector of
uniquely corresponds to the nullvector of fR.
In the latter case we know as a result of the fundamental theorem of 6.2
that the relation between Rand e established by T is a onetoone correspondence or isomorphism. The collection of vectors 1 of e which correspond
to vecton .J: in It do not have to fill up,the whole space e, but only a subspace
e' which is isomorphic to It and invariant under the transformations of!f,This isomorphism has as a consequence the reversibility of T, i.e. the exist
ence of Tl or the mapping of e' upon Il.
17Jeorem 11. If '6s is also irreducible, e' is identical to e and 8l is is0morphic to
They have the same number of dimensions and (3.11) can be
written as
e.
As == TA.R T 1 ;
Bs == TBR T 1
....
ffs
= TWa T 1
The two systems {#s and ~R are equivalent. They transform into each other
tIt
== '6s ==
(f,
then
AT
== TA; BT=TB;
7)ze matrix T commutes with all the matrices of the Irreducible system 'if
,and we will show below that this matrix is necessarily a multiple of the unU
matrix in " dimensions, or T = A.I, A. being a number.
Let us consider the equation Det(T AI) == O. This equation will have at'
least one root which is unequal to zero. Let us use this value for A.
The matrix T 1 I will commute with all the matrices of the system !f;
for every value of ,t since T commutes with all of them. The preceding the<)l
rems confront us with the following alternative, either T  AI establishet!
also a 9netoone projection of It on and the Det (T lI) 0, whic~
is inlPossible, or T  A, I == O. This establishes the theorem.
SummariziD, we have: A matrix T, which commutes with all the matr~
of the trr.ducible rep,uelltatlon of a group t, is necessarily the multiple of ~
unit matrix. If the matrix relates two nonequivaJelJI irreducible l'epresenta(iold
Ch. 3, 9, 10]
CHARACTERS OF A REPRESENTATION
85
like the relations (3.11), it is identically zero, a statement of major importance in the theory of groups and quantum mechanics.
If the representation is reducible we can easily construct a matrix which
will commute with all matrices of the representation and which is not a
constant times the unit matrix.
Suppose the reducible representation is transformed by a similarity transformation S to a set of stepwise matrices. We construct a diagonal matrix T
that has elements 1 1 , at the places which correspond to the diagonal positions of the first box of the stepwise matrices, elements A.2 on places corresponding to the diagonal elements of the second box, etc. This matrix will,
according to the previous theorem, commute with all matrices in the
representation presumed above. If we bring the reducible representation
back to its original form by the transformation 5 1 and if we transform T
simultaneously, the commutation relation will be maintained and the matrix
T will not be a constant times the unit matrix, provided of course we take
11 #: A2 :p
Hence we find that if matrices exist which commute with all the matrices
of a certain representation and if they are not proportional to the unit matrix
then the representation is reducible.. If they are proportional to the unit
matrix, the representation is irreducible. This forms a simple criterion
about irreducibility and it will finally lead to a prescription for finding the
irreducible parts of a reducible matrix system ( 12.3).
Tr A'
= Tr A;
Tr B'
= Tr B; ....
The trace of a product of two matrices is independent of the order in which the
matrices appear. A similar. statement for an arbitrary number of matrices
holds only if" the order is changed cyclically, which gives
TrSAS 1 = TrS l SA
= TrA.
This proof is only valid for finite matrices; in the case of infinite matrices we
have to consider the convergence of the sums.
86
GROUP THEORY
[Ch. 3, f
to
We will designate the character of the matrix A by X(A). ~Its value depend.
on the particular matrix we have selected, just as a function depends otithe
chosen value of the variable xs
The characters of the matrices representing operations belonging to the
same class (in the sense of 4.2) are identical as they can all be represented
in the form SAS 1 (S runs through all the representation matrices of the
group) and Tt S.AS 1 = Tr A. For this reason the character is said to be
a function' of a class instead of a function of an element as was suggested
above.
If the representation is irreducible the character is called primititie. 1
Let t: be a representation which is decomposedinto its irreducible elements
(3.12)
where the integers ml indicate how many times a particular representation is
contained in ill. The representations 'lI 0, 'lJ 1 , are not equivalent.
Obviously the characters have a similar relation
(3.128)
The symbols X o , X t , ..... designate the character systems of the irreduci
ble'" representations, i.e. the set of characters X o('')' Xo(B)~.". Xl (A),
X 1 (B)'i ... etc. They are different only if A"and B are elements belonging to
differe~t classes. Therefore the number of relations (3. 12a), which are distinctJ
is the same as the number ofelasses. We will see below ( 11) that these
character sets satisfy a number of relations between themselves.
10.2. THE NUMBER. OF IRREDUCIBLE REPRESENTATIONS OF A FINITE
GROUP
We have seen the importance of the notion of irreducibility in the preceding paragraphs. (A crucial theorem which we will prove in 11 brings
this out very clearly . )
WeJmow that an arbitrary representati~n of a given group f can 00.
posed accordina ~o (3.12) into its irreduci~le parts. These irreducibl~ ~~s
may differ from one arbitrary representation to another and there seems to
be no limit to the number of possible ineducible representations resulting
from these decomposltions. Actually this is not the case.
decQ,,
1 Some authors, comp. e.g. VAN DBIt W ABltDEN [1949] reserve the word character Cor the
irreducible representation 'Qnly and use trae. or spur otherWiset
Ch. 3, 10)
87
CHARACfERS OF A REPRESENTATION
o 100
1234)
(
P  2341 +
0 0 1 0
0 0 0 1
1 000
This matrix contains only one unit element per row and per column. The
permutation induced by the multiplication by a given element and repte$enteel by this type of matrix is called the regular representation.
, In order to establish this idea in a more formal way we let a variable x"
and a basis vector, correspond to eacb, operation s of a group. The collection
of v~ors s spans a new space Pt the socalled group space, which has 9
dim~sion8 in the case of a finite group of order g. A vector .: of this space
can be written as follows:
(3.13)
;: r,,., xllY,n
represents the basis vector that corresponds with the operation ST of the
&roup. The expression (3.14) may be read either as a double sum or after
rop1aci.ng the products by the proper group elements as a single sum in
which each element is repeated 9 times.
88
[eb. 3, 10
GROUP THEORY
(t
(IS
+
e'
Ae
= Lxsas
s
L,xattt.
t
of the operations
and s and we
have s = A 1 T) ..
The collection ofprojections or mappings A/orms the regular representation
of the group.
Let us: designate the components of ~' by x~ then the preceding equation
is equiv~ent with the set of substitutions
t
= a, b, c, " ....
= (a ts)
= (<>$tO1t)
= (Ja
t .'f
1)
l3.1S)
in which the rows and columns are labeled with the help of the elements
of the group themselves: E, A, B, .... S . T . and h",ts1 is equal to 1 if
A = TS! and zero otherwise. The matrix contains mainly zeros and only
a single 1 per row and per column.
If we return to the example of the group 9' 3 of permutation of three
objects, referring to its group table displayed in 2,,4 (second form), we
see that the~D:iatrjx A that represents the abstract element A is the following
1
2
SUIt) 3.nd.
ORTHOGONALITY RETALIONS
89
arrangcl11ent of 0 and 1
A=
001000
/ 100000
010000
000010
000001
000100
The importance of the regular representation is due to the following theorenl. All irreducible representations of a group r9 can be obtained by reducing
its regular representation ~,. . The number of times an irreducible representation appears in the regular representation is equal to the dimensionality of the
matrices of that jJarticu/ar representation.
The proof of this theorem can be established directly from the result in
11.2.. [Compare problem 3.8 where it is explicitly indicated that one
can obtain this proof from (3.23).]
1'\aklng up again our example of Y3; if one would reduce tile regular
representation of this group, one vlould find tIle unit representation once,
the alternating~ onedimensional representation once, and the irreducible
twodimensional representation mentioned in 7.4, twice.
Let r! ~nd t' be two irreducible representations of the finite group t and
(alk), (aik) their representation Dlatrices; nand n' the order of these matrices.
An important case is the one in which t' is unitary, but first we will deal with
the g~nera1 case. Consider a rectangular matrix S = (S,p.) with n rows and n'
colurnns and let us form the sum
(i)
extended over all operations A of i .. (The number is of course equal to the
order of the group g.) T wiU be, like S, a rectangular matrix with n rows and
n' columns. Let us write this ex:pression explicitly:
tile
1 ).
I'
~f
cOJLresponding to an arbitrary
90
GROUP THEORY
[eh. 3, 11
eTC; 1
:;;::
L C~4SA'IC'l,
.....
,
if we call CA == D, then A  1 C,1 == (C' A')l == D,l and D and DI
correspond .in _ and !l'to the same element D == CA of rI.
If A runs thro,uah the group (I, i.e. represetlts successively all the operations
of f#, D  CA. goes through the same group, but in a different orda (the
same idea was used in 3.2).
Hence
(,"'TC,l ==
DSD,l ==
ASA.,l = T,
which proves (ii).
For arbitrary c the result
.0
:s
CT
= Te'.
(ill)
If we apply now Schurs' lemma we find that either C and C', i.e. !!I and {I'
are nonequivalent and hence T :5 0, or t'6 and "lJ' are equivalent and T is
a constant times the unit matrix.
Flrs_ Case: t'6 and t' are nonequivalent; (i) gives
L ASA'l
==
o.
S"1
we obtain
(3.16)
and in the unitary case this means
r aUca~! = o~
(3.16a)
In the relations (3.16) and (3.16a) the indices i, k, v and l are arbitrary,
i.e. we ~."an arbitrarily located element in the collection of matrices, and
keep the position fixed in going from one matrix to the other. These relations
are important since they characterize the inequivalent representations.
SeCiJnd Cafe: 1M and t' are equivalent. We can choose a new coordinate
ORTHOGONALITY RETATIONS
Ch. 3, 111
where
= 'li.
91
L r. ausJt ali
JIt.
= tXbn ..
A.
Since the matrix 5 is arbitrary, let us suppose that all the elements are zero
except one of them sJt == 1; the preceding equation then becomes
(iv)
where the constant tX, determined by the choice of S, i.e. by the indices j a..s~d
k, is independent of i and I. In order to determine C( we have by definition,
(v)
(The reader should not confuse this summation, which is extended over then
dimensions of the representation space, with the summation
extended
over the 9 operations of the group ~~)
In eq1.lation (iv) let i == I, and if we perform successively the two summations with respect to the indices A and i we find, taking into account (v),
L.
~
L
i m. 1
.J.a:~
,.,.~ 1 :::r:
) ' (I"
.;.J
rlrx = .al5LJ
",~
A
}~
or finally,
L llikaki
~ gJll.
In case the representation matrIces are unitary the equations take the form
L a,t a;, == 0
A
and
L al1,a: == gIn.
(3.19)
The equations (3.16), (3.17), (3.18), and (3.19) are the basic orthogonality
relations bet}veen irreducible representations. The use of the term orthogonality
will be explained in the remaining part of this section.
92
GROUP TIIEORY
reb. 3, 11
L aiia~
= gin.
Hence using the right side of (3.19), we have the following relation bet'~leen
the characters of a unitary irreducible representatioll
(3.20)
Similarly if we deal with
find from (3.16):
t\VO
L X'(A)X*(A) =
o~
(3.21)
X =
L X(A)
It.
.Jg:
L
A
.!Jg.Jg
1 X<P)(A) .
rt1)*(A)
ODg
(3.22)
Ch. 3, 11]
ORTlfOGONALITY RELA1"IONS
93
of each other. The same holds for the matrix elements ail" ail Of,
according to (3.16) for aik, a~.A. ..... 1
Similar statements can be made for continuous i.e. (infinite) groups. For
example if we have the group of rotations around an axis, equation (3.22)
becomes the wellknown relation
2n
0mm"
(3.23)
and
1 .t...J
'"'
g
X ("
A)X*()
A
==
2
111.0fm 21
+ .... ,
(3.23a)
! L X'(A)X"'(A) =
9
1,
We have mentioned in 10.1 and 10.2 that the characters are functions of
a class. WewiU indicate the p classes into which we can subdivide the group
t: by C 1 ,. C 2 , C 3 , C i . Cp Each class contains Ill' hz, hi, .. " ., hp
Compare problem
s.
94
GROUP THEOR.Y
If we introduce X,
written
[elL 3, 11, 12
1' ....
,, _ _
,=L1 XiX: == 1
and
L X;X: == o.
(3.24)
fa 1
t\
..
...
111#
e.
=::=I
AU)
1
+ A(2i) +
A( I}
II,
(3.25)
where".'~
(3.26)
To show this we take the conjugate of the lefthand side with an arbitrary
SUM OF A CLASS
Ch. 3, 121
95
element x which will only permute the elements in each sum of a clasa. As a
result the righthand side will never contain a set of elements which do Dot
fill a whole class, because all possible conjuptions would generate the miasing members of that class, and because the lefthand side must be invariant
under any conjugation .
The coefficients Cal' which can be determined from the group table, reflect
the structure of the group_ With the help of these structure coeffjcitmt8 we can
determine the character of all possible irreducible representations of a given
group.
The hypercompl~x numbers C, formed by the sum of a class commute with
all elements of the group, since
(3.27)
where x is an arbitrary element of the group; XI c,x = c, because conjugation only permutes the terms in the sum accordina to the definition of a class.
If we now take the representation by matrices of (3.26) and apply one of
the theorems of 9, we conclude that these matrices are constants times the
unit matrix i( the representation is irreducible. (It is not di:fftcult to obtain
the explicit value of this constant but its value is not needed for the following
argument.) If two matrices are multiples of the unit matrix the product of
their:traces is equal to the trace of their product times the dimensionality of
the matlrices.
Applyi~ thls to the matrix representation of (3.26) we find that
,.
h,Xth1Xi; == n 12 cUt1h,X,
(3.28)
11
96
[eb. 3, 12
GROUP THEORY
r'
p=l
lt
),
(3.29)
1=1
r'
L n{p) X1/l) = L
,,=1
JY(Il)(E)X<p)(C ).
1
1'=1
This is simply a change in notation since n is the dimension of the representation and X(E) the character of the unit representation. However, according
to problem 3.8 the characters thus obtained are the characters of the
regular representation, and these are all zero, except of course if c, = E.
We find
r'
since the dimension of the regular representation is the order of the group.
Substituting this into (3.29) we obtain:
r'
L X<1t)(Ci)X(P)(C;l) = g/h,
(3.30)
,.::01
Cr
1
The symbol
indicates the sum of a class of elements inverse to the elements in the class C,. This may be either the same class or a different one.
In bot1), cases it will contain the same number of elements.
If th~ representation is unitary, we have
I
,,'
L X*(p)(Ci)X(Jl)(C
j)
nlht .
p=l
L h,X*<P)(Ci)X(Jl)(C
j)
= g,
(3.20a)
i=l
but is entirely different in nature. Equation (3 . 20a) contains a sum over all
classes i = 1, ... r while (3.30') contains a sum over all irreducible representations p. == 1 . . . r'.
The theorem is now easily proved if we consider the double sum
r
r'
L L h,X(")(Ci)X<I')(Ci )
i=ll'=l
== gr = or'
SIJI\;f OF A CLASS
Ch. 3, 12}
97
I~i~
p=l
.~t=2
i~i. ~:: 3
1
1
2:
I.
I
i l l
II
1
1
I
 1
()
KOSTER
[1957].
I
x;
.
xx
X
f~~r'
'
......... ..,
...
\\
l xxx
I '
!.
lxxx/
,
I xx x
_. . . . .~~ __ ~~ .. ~ .. _4~
_ _. _ .
i xx t
""'
""
/ 00;
! ...xx;
..... ...........................
00 i
x .......
x ~,I..............
........f~ .
i
.~
; 000
.~ 000
000
This DJ8trix has zero elements except at those places on the diagonal which
corre~pond with the box we want to "project". The irreducible representations can be considered as "components" of the reducible representation.
The projection matrices 8 are also referred to as idempotents because they
have the p~operty elt = B for any power 11.
The result at the right..hand side is a set of matrices that are again isomorphic
(or homomorphic) with the group_ They form an irreducible representation
if we omit all superfluous rows and columns (those that contain nothing
but zeros)~
If the representation was not in box form we could bring it into this form
by a. transformation A ~ S 1 AS ~= AD" The representation in box form is
designated by a superscril,t h. Conversely if v{e consider the inverse transfor':'
mation applied to the equation
.
(3.31')
[Ch. 3,
GROUP THEORY
12
= SA
b (Il)Sl
or
e(PJ,A
==
..4(11).
(3.31)
=:
(n,t/g) L X:(i)C,
(3.32)
where 9 Ul the number of elements of the (finite) group, nil the dimensionality
of the itreducible representation jJ., .U the characters of this representation.
The s~ is taken either over all the matrices that form the reducible representation of the group~ or as the right. .hand side of (3.32) indicates the sum
over all C i Since the characters of all elements are equal as long as they
beloJig to the same class it is obvious that the second sum is identical with
the. }first~ provided the representation is unitary.
'The matrices 8(") can be constructed in a straightforward way from a given
representation if the characters of the irreducible representations are known ..
These can be calculated from the structure coefficients as mentioned in
12.1 and these in turn follow directly from the abstract group table. U"uq.Uy,
however, the necessary character tables can be found in the literature..
If a calculation is perfonned t it is of course advisable to investigate first
whether ~p.reSentation Jl is really contained in the irreducible representation..
This cati'be done with equation (3.23)~
<Finally we hav~ to demonstrate that the products 8(1') A really form for
all A an irreducible representation p.. The necessary and sufficient condition
is that the chat1h,.~ers of 8(1') A are equal to the characters of the irreducible
I
Su~J
Ch.. 3. 112]
99
OF A CLASS
representation Jl
(3.33)
AI
==
8(1'),
s(jJ)
C I.
=:
nfJ.611., ..
(3.34)
(We must assume that A contains the representation v only once.) From
this we conclude that
c :: 6". ~
(3.35)
If if is reducible and in box form, the matrix a(}l) will be a diagonal matrix
with the diagonal elements zero except at the places corresponding to tho
box p., according to (3.35). If the representation is in box form equation
(3.33) holds. But then it should hold for any representation, because tho
characters are invariants.
The p~escription for performing a reduction is the Conowin&. We have a
set of basis functions and operate with t.he prescribed operations of the
group in: order to create matrices. Now, depending on how complicated the
problem is, it might be worthwhile to see which representations are contaiiled
by taking the trace of each matrix (one of each class is CllOugb, if the classes
were not known this is the moment to find out) and determining the coetTicients in eq. (3.12a)
If a certain irreducible representation is contained one constructs the
projection operator (3.32) and inspection of these matrices usually tells us
which rows or columns are supet;ftuous.
If not obvious we mUltiply the projection matrix with the basisl! The
resulting linear combinations are either zero (in case a certain row contains
nothing but" zeros) or partially dependent on each other. We take from each
set of dependent linear combinations one and drop the othen.
As an epilogue we should like to point out that the idea of projection
operators is solely based on the theory of characters. First, the only reason
~
100
GROUP TfIEORY
[ell. 3, 12, 13
that the projections (!/p).4 are the ll1atrices ~Ne want theln to be is that the~
have the proper characters, and that fact is sufficient for irreducibility.
Second, the way the operators G(p) are constructed is to make use of the
orthonormality of character systenls, and this was used (3.34)"
If a certain irreducible representation is contained several times. in a
reducible representation!t one has to proceed with more caution.. In this case
the projection will result ill a linear combination of the multiple occurring
representations. It is necessary to perform an additional orthogonalization
in order to obtain the box form. "There is an arbitrariness in this procedure
similar to the arbitrariness in tIle choice of orthogonal wave functions
in a degenerate eigenvalue problem~
In the important case that the reducible representation is the product of
two irreducible representations of the rotation group, the method does not
apply, because these are continuous groups. This case can be treated in an
entirely different way (Chapter 5 : 5~3).
13. Representations of the Permutation Group
13.1. YOUNGTABLEAUX
In the special case in which we are dealing with the permutation group it is
possible to obtain irreducible representations in a clear and concise way.
The ideas explained below are originally due to A. Young, WilO published a
nu~ber of papers on group theory around 1900. 1
If! we consider an element of the pernlutation group and if we employ
the hotation with cycles for instance,
(3.36)
(3.37)
Ch. 3. 131
101
Every row corresponds to a cycle and hence the numbers in a row can always
be cyclically permuted . It is the custom to draw the different cycles in decUma,
order, that is to say the first row is the longest cycle, the second is either t4e
same length or shorter, etc. If there are two rows of the same length the order
in which they are written is irrelevant. The shape or contour of this scheme
determines a class of equivalent permutations. (Compare the end of 5.2.)
This is a onetaone correspondence. If two schemes are of the same shape,
they belong to the same class of permutations and if they are not the same
shape they belong to a different class of permutations. By the shape we mean,
of course, the'empty box, i.e., the tableau without the numbers. Instead of
describing the shape or the class of permutations by indicating the length of
each row or the length of each cycle, one can do just as well by telling how
many cycles there are of order one, how many cycles there are of order two.
how many cycles there are of order three, etc. The number of cycles of a given
order, that is, the number of rows of a given length, is sometimes called the
rank number. If n is the total number of elements which we are permuting,
we have the following equality:
(3.38)
where the rank number at indicates the number of cycles of order k.
The number of permutations that belong to a class C{.,} characterized by
the set of rank numbers Ql,. Q2' 03 t ~ a" == {a i } is equal to:
(3.39)
The derivation of thls formula is easily demonstrated with the help of example (3~16). If we take the corresponding Young shape we have h, i.e. in this
8 open places and hence can fill in the numbers in 8f (h!) different ways.
The nWIiberof rows of length k is ai and they can be permuted in any order.
Hence we have to divide the total number of ways hI by al! in order to get
the total number of classes. Now we can cyclically permute all the numbers in
each one of these rows which gives a factor kale since each row allows k
cyclical permutations. That means JcD"a,,! in our example (3.37) 3 for the
first row and 22 21 == 8 for the next two rows. The number expressed by
(3.39) is found in different places in mathematics and physics. In the theory
ofnwnbers it is called the partitio numerorum, i.e., the number of ways one
'tan assort a certain number n, of objects into piles with al piles of one object,
a2 piles of two objects each, etc . To physicists this factor is vleIl known from
cUe
GROUP THEORY
102
[eh. 3. 13
We will introduce a special set of elements which will eventually lead to the
construction of an idempotent.
Conjugation oean arbitrary element T with respect to p (i.e. TJ = p1 TP),
will have the effect that the Young tableau of T will maintain its shape. The
numbers in the shape will be permuted in the way described by P. We consider
only the elements p which will create a horizontal permutation in T. That
is to say, the numbers in one row will be permuted but will never leave that
particular row. Such elements form a subgroup_ We will call this subgroup ?I
and its order is equal to nta,,! (Compare Fig. 3.6 for the general Youn,
scheme.) Not all elements represent different permutations. In a similar way
one can introduce those permutations, which, if used. to conjugate given
permutations, create permutations only within a given column. We call this
subgroup !2. Any rearrangement of numbers in a given tableau, i.e . keeping
the shape the same, corresponds to a similarity transformation
_1
Pop T = P
(3.40)
TP.
(3.41)
is an element of i?,. either a reducible or irred ucible representation of this
element. or, in the true sense of group algebra, an abstract element. The
R.
number$/{(lt) are:
OifR:;'PQ
'(R)
=(
1 if
==
PQ and Q is an
 J if It PQ and Q is an
R.
even permutation
odd permutation.
(3.42)
Ch. 3, 13]
103
'
"?
~
104
GROUP THEORY
rCb. 3, 13
L C(R)C(R IT)T.
(3.43)
With the help of the result (3A.6) of the Appendix to this Chapter we find
{2 == pC and with
pt C == 8
(3.44)
we have 8 2 := 8. The number p is a real integer as can be seen from the derivation in the Appendix.
The fact that the , is aD essential idempotent allows us to use this operator
as a projection operator. Any idempotent a CulfiDs the equation ';8 =: 0,
hence the idempotent must have eigenvalues 1 and O. If we multiply the
matrix 8 with a set of basis functions, all components that correspond to a
zero in the diagonal of the amatrix will be removed. Hence the number of
independent basis vectors is reduced. If the 8 were Dot in dia,onal form
the last arpments would still hold as we have shown in 12.3. An obvious
aspect of projection, viz. projecting twice gives the same result as projecting
once, is automatically fulfilled since 8 2 == 8.
13.3. IRllEDUCIBLB REPRESENTATIONS
elements as ,above, or as a set of matrices EI, Aa, Be, ... , Sa, ... where 8 is a
matrix 'which bas the property that the eigenvalues are either zero or one.
Apin, this cJ.iatinctjon is ~levant but wo wanted to make it clear that the
projection...operators are written on. tM right. 1
1
at the left by the hypetCOmplex numbers or the _bra form a subset or the allebracidtoCl
tho left ideaL In this language the minimal (simple) left ideal corresponds to our irreducible
representation.
Ch.3 , 13]
105
s + ASs =
A
La C(R)R
(3.45)
is represented by a matrix:
= T and
the trace is
we calcate the sum (3.23a) and show that the righthand side is equal to
one~ USing (3A.7) we find indeed
g1
(3.47)
'"
~i
~'
106
GROUP THEORY
[eh. 3. 13, AI
r~'"
l_J I
I
I
~
11J ._
r1
I
L~
rl
~lI
.,.
~,l
IL
1
____:l
The plus sign indidates a direct sum of t\VO permutations. This ide;a is
extens~ely .'used' in electronic and nuclear spectroscopy.. If one wants to
find tlte;,. ,.>';
~.Jtevels. of a nelectron system from the knowledge of the
wave
and energy levels of a n  1 electron system. In such a proce~
dure it is necessary to form products of linear combinations of wave functions but not aU of these products obey the Pauli principle:. Hence one is
interested in only certain representations of the permutation group. In this
case the pennutation is with resfJCct to tIle electrons .
~
" ~:;.:!+.l'
"?:
In order to prove the equation mentioned in 13.,3, Vie study the properties
of th.e hypercomplex numbers C (compare MOLENAAR [1930]) . First of aU
\ve notice" ~that
((E)
1;
C(p) = 1;
'(Q):;~
Ch. 3, AI]
107
APPEN11IX
t(PR)
since either R
::; PI Ql
(PR)
==
(3A.3)
'(R)
:=:
and according to
~.
(3A~1)
we
$"
ha,;I,;~:
'*
or R
Pi Q1" In this case the righthand side is zero . 1~h(~ Jeft. band side is also
zero because PR =F .P P l Ql is also not a product of a .P and a (I . Hence the
second possibility satisfies the equation as vFelL
Following the saIne line of reasoning one can ShO~1 the relation
(3A..4)
since either
R ::..~ PQ,
'(RQ)
= (Pl Ql Q)
= {(Ql)C(Q)
L ((APB) = L '(AP)'(~)4
P
Either: B
= P 1. ()t
(3A.5)
L C(AP)'(P 1Ql)
p
:=
L C(AP)'(Ql)
p
Or if B ::/.:. P:t Q i the right..,h.and side is equal to zero and since according to
the second criterion B 1 PB and Q h.ave a transposition in (~ommon: Qz =
l
B P2 B Hence replacing p by PP2 in the sum 'we have
f!
.,
2: '(APB) =  L (APB).
p
=:
1 and
[eh. 3, AI
GROUP THEORY
108
(3A.6)
It
by
p1 lt
(3A~5).
The number p represents the total number of elements that have the property
that they only create horizontal permutations in t]le tableau. If we replace
It by PR then we have
PLC(R)C(Rt){(T)
== L_C(R),(a 1 ).
The
la.~t
over P, we obtain:
PL == LLLC(SlR
 l p 1
S)'(PR)
L L L ,(sl a  lp l)C(s)C(a),
F
..
== p}2 L C(Slltl){(S){(R)
R
apin using (3A.3). The result ist that by replacing s by ps and summing over
P, we will have:
APPENDIX
Ch. 3, AI]
109
using (3A.5) and (3A.3). The sum over P can be performed by replacing
s by PS and \ve obtain, using again (3A.3):
P
CHAPTER 4
GENERAl.; APPLIC.t\TIONS TO QUANTUM 1\IECHANICS;
~
"TIGNER'S THEOREM
1. Invariant Properties of the SchrOdinger Equation
1.1. THE T\V() GROUPS OF THE SCHRODINGER EQUA'rION
'There are two important groups that leave the Schrodinger equation,
Lt~", the Ifamilton operator II, invariant.
1, rfhe p~rmutation group  the exchange of positions in space  between
identical particles, either electrons or nuclei. This group will always leave H
invariant . The quantum theory makes the fullest use of the indistinguisha[,ility of identical objects.
2e 'The group or rotations and reflections. This group plays a role only if the
potential energy has certain symmetries.
l'hese groups are related to the space coordinates of the constituting
particles only, i.e., their operators are orthogonal linear substitutions in the
conJiguration space (the axes in the ordinar.,v space stay rectangular)~ They
occ"hr in ordinary as well as in relativistic mechanics.
The Lorentz group which acts in spacetinle, does not leave the Schrodi.Jiger equation invariant, but only the Dirac equation .
1.2. TRANSFORMATIONS INDUCED IN FUNCTION SPACE BY THE. TRANS..
FORMATIONS IN CONFIGURATION SPACE
If Xl ~ X2, " " Xn are the coordinates of the particles, Le~, the coordinates
in the configuration space r and if s represents an operation of one of the
groups we mentioned (for instance, a rotation of the entire helium atom
aro\lnd its nucleus, or a permutation among its electrons, both of which
can be expressed in sixdimensional configuration space), then s can be
expressed by' a system of 1'1 equations
n
x; = L UikXk,
(4.1)
k==1
wher~
the matrices cr are always orthogonal in the real sense of the word.
110
Ch. 4, 1]
INVARIANT PROPERTIES
III
sx;
X' ::
S 1 X'
(4.1a; Ib)
where % represents the set of coordinates Xl .... x,., i.e., a point in the configuration space.
Wh..t are the repercussions of the operator s in the function space or
statevect<;r space _1 Or according to the language of H.. Weyl: "Which
transformation induces s into the space Ul?"
Generalizing the statements of Chapter II 3.2: The operation s substitutes
in rspace the point x' = sx for the point x and at the same time carries
the value the function ..p had at the point x to the .point xl'. We may use the
follo"ring picture. The operation creates, so to speak, a redistriblltion of the
wave function distribution in r . . space as one redistributes the masses in
ordinary space if one describes the motion of a fluid. The coordinate system
being fixed, we obtain in this way a ne\v wave function ""(x) and we have
by definition
(4.2)
tfJ(x) + ifJ' (x) = sfjJ(x),
=:
s.jt(sx) = tjJ(x)
(4.2a)
or
(4.2b)
In the equations (4Q2) and (4.2b) the elements s of the group ?J can be
considered/as operators acting on the vectors or rays of the function space,
as mappi~gs of the space 91 on itself, or as mappings induced in the space m
by the group ~.
We can easily see that these are linear. They are unitary since we have for
two functions '" 1 and t/12'
(1/11
==
(s!/ll Sl/J 2)
all
orthogonal transfor
GENERAL APPLICA'fIONS
112
t.
[eh. 4, 1
and since s is an arbitrary element from the group ! we may write accordin&
to (4.2b)
(4.3)
i.e., the operation s does not change the function V. We \. a,all say that the
functions which satisfy the condition (4.3) are symmetrical with regard Itl
the group '6 or invariant under the operations of the group ~~
If we consider the product of two functions, for example, V and 1/1.,
we have according to (4.2b)
s[V(x) y,(%)]
= V(Sl X)I/I(S1.x)
== sV(x) . s./I(x),
and if
.,P is invariant
s[V(x) "'(x)] = V(x)s.p(x).
0
sHtJ!
:=
HstJ!
usually done in the theory of operators, we omit the object ./1 on which
theyi operate and write
sH :r= Hs.
(4.4)
Of, 8rS
(4.5),
The equation (4.4) shows that the operator s commutes with the Hamiltonian. If we remember the quantum mechanical meanina of H(H = ilia/at)
we see'that the operator S dOes not chanae in time. Considered as a physical
quantity (for this it has to be Hermitian) this opefa.tor is a constant of the
motion~ The same conclusion follows immediately from the equation (2.27)
of Born, Heisenberg and Jordan.
This remark is the basis for the quantum mechanical derivation of the
classical theorems about momentum. (Chapter S, 3.)
Ch. 4, 2]
113
WJGNER'S THEORE?vI
2. Wigner's Theorem
2.1. THEOREM
z: "'/eSt;
IX
SI/Ji
(4.6)
k==1
In the same way each element s of the group gives rise to a matrix S == (Slti)
ofotder the elem~nts of which are generally complex numbers. The whole
set o/the matrices or the whole seto/the traM!ormations (4.6)form a representation of the group
To prove this let
9)"
be another element of rJ
(4.7)
It
114
reb. 4, 2
GENERAJ.J APPLICATIONS
or according to (4.6),
L (if!
j'
t/ll)S1t s!k =
j, I
Hence
=:
O;k
)1
"s*s = ()~ ik
4i
Ii
LJ~
s*s =
I ..
tha~
IX
i/I; = k=l
L "'leakl'
the matrices S become
S' == A1SA
SX, =
L X"Sk
(4.8)
li
Th.e elements St,t , Hid are complex nUDlbers and not dependent on
time.
Let us suppose that s, T ... are the elemellts of a. group c. The matrices
S' == (S".), T' = (Tii)t . (primed in order to distinguish these matrices
from the finite matrices S ~d Tused in the first part of this section) form a
representation t' of t of infinite dimension. This representation is unitary if
the group f is unitary. The proof is the same as above (compare (4.7~
Let us reduce 16 in its irreducible elements
"
(4.9)
In this series we will find sev~ral times the same irreducible representation,
often even an infinite number of times. The reduction is obtained by a unital:y
Ch. 4, 2]
WIGN!3R~S
THEOREM
lIS
change of coordinates, Le., by a clloice of new axes lfJl, lfJ2~ which are
suited to the problem. Thus each matrix takes the box form corresponding
to (4e9)
o ....
o . ., . "
0
S1 0
0 S2 0 .. . .
T=
0 T2 o ...... ,
(4.9a)
0 S3 .... *
0
0
0 T3 . ~ .
(Tl
s=
where S 1, Tl
1#
..
"
..
..
\~
..
..
..
..
of the representation
Cfi 2 ,
In other words the orthogonal functions <P, are arranged in partial sets each
of which span an invariant subspace of the function space 91.
The Hamiltonian H is, however, not an operator of the group rI. The
matrix which corresponds to this Hamiltonian in the systelD of axes can be
,,'Iitten as follows: all the matrix elements connecting the functions of one
subset to another are gathered in a unique symbol
H=
HIt
HI2
Ht3 .....
HZ1
H22
H 23
H3t
H32
H33 ..
..
..
.. ..
(4.9b)
4>
where the H fk are submatrices . Most of them are rectangular, for the different
boxes S, T. ... do not necessarily have the same dimensions.
Let
form the products HS and SH (when multiplying two matrices
the submatrices are dealt with as matrix elements).
us
H i1 .S1 ~
HnS z \.
TJ. 3Z S: ..
/II 1i S t
HS .....

~H11S1
8
."
31 8 1
..
"
.;r
SH
/S1 11 11
(S2 H 21
S3 R 31
\.."
S!HI2
S2 H 22
SJII 32
SlH 13 ~
... )
S2.1!23.....
S"!,H:13 I
to
""...1
!.e.
Schurs' Lemma can now be applied and it leads to the fol1ow"ing conclusion
l When Si and S" are unequivalent Bik :::::: 0
2 \Vhen ,S i is equivalent to Sit; ~ f1!k i;; a multiple of the unit mattlX and
~te havt!
116
feh. 4, 12
GENEllAL APPUCATIONS
the S
matri~"
.1 n,
t
times, etc. . .. The matrices (4.9a) and (4.9b) take the form
80
'0
0
<It
(4.13)
'0
"
$,
$2
lIa1 (0)
<If
"
.,. (0)
lIa. (0)
"
"
\
0
...
H
(4.
N11
cn
1121 (1)
"21
U)
"22 (1)
.....
..
.. "
if
,.
."
Ch. 4, 2]
117
WIGNER'S THEOREM
are
HUc(l) = H;k(/)1
(4.11a)
\Jl
118
GENERAL APPLICL\TIONS
[eb. 4, 2
m,.
It,
,
i
~"'~
\
,
\\
!f ~'
12
lill
... f
'. i
.~...~H;.
0
H4~
(I
I
H
LI'
i
~
'. . , "
1
j
a1 '.
)1
"12"
',.
' . I
,I
"4':"+~
a set of axes "'.,. which are eigenvectors of HI' These are the :.
ei&enfanctions of the Selttadinger ~quation.. The matrix. (H!t{l)) of dimension;'
", ~mes diagonal, To each of its diagonal elerrlents Enl which are the.
enersy 'evels of the system) there corresponds a subrrtatrix in H, which is a
multiple of the unit matrix E",I, of the same dimension as raJ. Thus we
obtain, after bringing roY's and columns in their original arrangement,
I
'.
,
\
'\
\\
119
Cb. 4, 2]
This matrix has clearly the same arrangement as the matrices S (4.13):
each of the big square matrices corresponding to an irreducible representation!, of ~~ntains as many small square matrices as t' contains 9i 1 i.e. nl._
The set of the elements included in a big square matrix form a term system
in the atomic case, i.e., a system with fixed Ivalue and different n. .values.
The combinations between the elements belonging to different tenn"systems
are subject "to selection rules which depend on the group (I (cf. chapter 5, 7).
It can be proved that they are not allowed if (9 is a symmetrical group.
It is easily seen that one can reduce H to the diagonal form (4.14) without
modifying the fonn (4.13) of the "matrices S  (see Appendix 1).
The equality of the values E", of E in each small square matrix comes from
the symmetry properties of H "ith respect to the group'll and forms an
essential degeneracy: it is impossible to separate the corresponding levels by
a perturbation W unless this one alters the symmetry of H. If W is invariant
only for a subgroup ,;tt' of 9J, the representations which were irreducible with
respect to f cease to be so with respect to .Yl'. Their reduction leads to a
separation of the levels coalescing in E". The eigenvalue spectnlm becomes
finer. 1 The energy levels are labelled with 3 indices or more instead of only
two. For example, this happens when a hydrogen atom is placed in an
external magnetic or electric field. The spherical symmetry is replaced by a
cylindrical or conical symmetry.
The preceding theory gives us valuable information on how to perform the
pertur~tion calculation. Let tX be the dimension of the representation 9J,
of 'I, ", (I == 1,2 ... ex) the eigenfunctions which form a basis for this
representation, i.e.. , which describe all the states belonging to the exfold
degenerate level
in the table (4.14). In order to calculate the first order
perturbation W, of this level it is generally sufficient (see Chapter 2, 7.3) to
solve a secular equation (2.47) of order a . In this equation only the matrix
elements Wit (I, k = 1,2 ... <%) resulting from the mutual interactions of the
E.,
But if we know the subgroup ,;tt' of 11 \\~hich leaves the perturbation function W invariant and the number Pof the representations resulting from the
reductions of t6, with respect to the subgroup JIf', then we know the level Elfl
is divided into only P < ex distinct levels and the order of the secular equation
is lowered from ci to p. Besides we know a priori the basis of the new repres~n...
1 The group tit' ja formed with certain elements of ., . Then the invariant subspac~ or
tho group !I remain a fortiori invariant under the elements of f but those sutotl'ac~ can be
further subdivided..
120
GENERAL APPLICATIONS
reh. 4, 2
Let us make a last remark, one which is almost trivial but which may
prevent misunderstandings. If we consider the equations (4.8) or (1.25)
literally we can think about the matrices S J of the irreducible representations
corresponding
,of ~ as matrices of rotation of the axes in the subspaces
to the small square matrices of (4.13). We su.ppose that the basis fUllctions
if/",. are known: i.e., we have:
Ill
.'/',
l'
m'
with
(4.88)
Ch. 4, 2, 3]
ABELIAN GROtJPS
We can also suppose the axes are fixed and consider these matrices as
mappings of the/unction space on itself Let'" be a wave function expanded in
a series of orthogonal basis functions,
JjI =
I,
L
II,
Plnm ~/lnm
We have
11t'
_. '\ p. t . j.
lm~' tp lnm' :;
 ' lnm'
with
 '"
L..J SO)
m'm f3 b,m
P'Inm' m
(4.8b)
This group !?'* contains only two elements E == (1) and s == (1 2) with
the only rule of multiplication S2 = E. In order to represent this group let
the element s be represented by a onedimensional matrix such that the '
number S satisfies the equation S2 = 1.. Thus one obtains two irreducible
re~ntations of 9'2: E, S == + 1 and E = 1, S = 1.
It follows that in the space of the states for an atom with two .eleotrC)Ds
(helium) tho matrix S of the equation (4.13) is decomposed in only hVo big
square mafnces: In the first one the number 1 occurs along the diagonal
(obviously they are infinite in number). In the second square matrix the
number 1 occurs in the same way. Once H has been put in the form (4.14)
we obtain
122
GENERAL APPLICATIONS
/100
010
II
001
fCb. 4. 3
II
.I
s=

(4.15)
....
0
0
o .., 1
1
0
o 1
1
i
II
"./
I
!
/E1O
0
o E,.o
H=
I
!
t
I
!
I
. I
I
.~
Ell
Ell
(4. 15a)
Hence, there exist two systems of eigenvalues corresponding to the two sys...
teDl.$' of eigenfunctions. One of them satisfies, after (4.1 S), the equation
sy,lt =
these are the symmetric/unctions. The second satisfies St/lk :=  "',,'
these are the antisymmetricfunctions. (We delete: with respect to the group
of permutations.)
"'i'
or
Ch~
3, 4]
123
ABELIAN GROUPS
X(rp)X(cp') = X(,,+cp').
=:
I.
eta(cp).
),(0) = 0,
A(cp+cp')
= l(cp)+.A.(cpf).
+ 1, :r 2 .
m = 0,
It
..
An atom in an external magnetic field has the symmetry of the group ~241
Every matrix S(cp), representing in function space a rotation q> around the
field, is decomposed acoording to the scheme (4'113) \\ith
St(cp) == e ifJ ;
So({J) = 1;
S~(<p)
= ei'P;
S;(~)
,S2,(q
= e2i ., .... ;
= e 2f. ;
1\
..
(/'0
:=
== 0
l/lm(r., rp, 8)
= e1mVI!rlr, 0, 9)
:=
e1ffUPt/lm(r, 8}.
124
reb. 4, 4
GENERAL APPLICATIONS
~2
2'
I  ,/~
I .I
.
I
II
!,
I
I
I
I
I
If
'
I!!
I!I
i
I:
i
f
One call go from the position 1 to the position 3 in two different ways.
A rotation sip (1 to 2) and a reflection T (2 to 3), or a retlection T (1 to 2') and
then a rotation
(2' to 3). Thus we obtain
s_.
where the succession of the operation must be read from right to left as
usual. First~let us consider the subgroup P)2 of ~;. It induces in the function
space a representation which we have studied in the preceding section:
the invariant subspaces are onedimensional and are spanned by a set of
basis functions t/J m' such that s(,p 1/1m = e iPJrrp t/I m. Let us suppose m > O.
Ch. 4, 4]
NONABELIAN GROUPS
125
stpV'm
.1,
_

1""1.1,
'i'm
TeimfPif.tm
Tt/I". = t/Im.
(4.17)
(4.18a)
Then the representations and the levels are classified according to the
absolut~ values Iml, +m and In being associated in the same representation. The eigenvalues for which Imf = 0, 1, 2~ ..... are labelled by the symbols
E, 1t, L1:t . . .. l~he state m = 0 is a particular case:
s"t/lo =
so(q = 1, as (4.16) gives us no more information To is
determined by the condition T2 = E, i.e., Ti = 1. Then we can take at will
"'0'
To =
+ 1.
126
GENERAL APPLICATIONS
[Ch. 4, 4
Appendix 4.1
"2m
S11
S21
Sui
8 22 1
I
S2
==
,..
S11
S121
S21
S22t!
f
1
H2
H21
0
=:t
H~2
H~l
0
0 . H~m
H;".
H~2 ~ 0
0
H;l
H;"l
H~l
. . .
that is t~ say that, if we designate the 2m basis functions by fPt, CPt, cpz, "2
lfJ""qJ:', the matrices S2 transform as:
(4.A2)
"
. . . .
..
. . .
..
..
z=
0Cm 'Pm
127
NONABELIAN GROUPS
Ch. 4. 4]
H 1 "" = (Pt H; 1 +
Pm H :"1)q> ~ +
+(P1H~2+
. fJ.H~2)<P;+ ....
We will reduce H2 to its diagonal form. and we will have H2Y,  E';;
H) t/!' == Et/I' if we satisfy the equations
cx1H t1 +a2H~1.. ".H:'1 == Ea 1
(XIH~2+(X2H22 tX".H~2 == Ea2
. . . . . . .
.. .
(4.A3)
..
H:"1
H 12 E
H:" 2
. . .
..
. . . . .
==0
to
CHAPTER. 5
1?}3
We will follow the historical order. Let us consider an atom with only
one electron in a central field of spherical symmetry (BohrSommerfeld).
We suppose that the origin of the polar coordinates Tt 8, tp is at the nucleus.
The potential energy is att arbitrary function of the distance r. The Schrodinger equation and the Hamiltonian H are invariant with respect to the
group Pl3 of the 3dimensional rotations about arbitrary axes passing
through the nucleus.
According to the Wiper theorem the eigenfunctions of this Hamiltonian
can be classified in a number of different systems. Each of them acts as a
coordinate system in function space and constitutes the basis of an irreducible
representation of the group ~3. In other words, each of these eigenfunctions
bcpomes after rotation a linear combination of functions of the same system
~ the matrices of these transformations form an irreducible representation
or; the group.
,/We shall show that the solutions of the hydrogen atom problem as
.c8Iculated by Schrodinger have this property_ These solutions can be written
as follows:
(5.1)
!
with
y,(m)
= eimfP(sin
(S.1a)
where Y,(III) is the usual notation for the Laplace spherical harmonics.
The associated Legendre polynomial is defined by
d(lm)
Pfm)(z)
= di 
(1 Z2).
(5.1h)
'
The Laplace spherical harmonic is homogeneous in cos 8 and sin 8. Its
degree I, the azimutluzl quantum number or the quantum number of angular
128
<"'h. 5, 1 ]
SPHERICAL HARMONICS
sm
Y,
Y,<"').
Thus the eigenfunctions t/I are products of two factors, the first of which
I.,(r) only depends 'on the particular interaction between the electron and the
remaining part of the atom; the secon9 one exhibits the symmetry properties
of the operator H with respect to the group ~ 3.
Since /",(r) is left invariant under an arbitrary rotation s of the system
about the nucleus we have
"'~~) + s"'~~) = !II'( r)s y/"')( qJ, 8),
but st/l~~ is also an eigenfunction of the energy level Ell" hence sYf) is a
linear combination of the (2/+1) functions Y,(lII)(m = 1, ..., +/):
p=+l
S y,(m)( qJ,
8) =
2:
y,(P) S~!
(5.2)
p=I
As x + iy
I in
x, y, z has the form: r' Yz(<p, if). Tbe YI("') are basis polynomials, homogeneous in x, y, z
and defined on the unit sphere by' the condition that the difference between the exponents
of (x+iy) and (xiy) be equal to m (cf. (S.la. The expansion or an arbitrary polynomial
n
Y, in a linear combination of (21+ 1) polynomials
) follows from this definition.
yt
130
[Ch~
S, 1
exp [ ilwg]
o
.
"
..
0
exp [ i(ll)coz ]
&
(5.3)
...
All the~ representations are of odd degree (U + 1). One can wonder why
this is so land if no other exists . According to Chapter 4, 3.2, concerning
the plane' rotations PAz, the exponents m of the exponentials exp (imt:z)
have to be integers in order to obtain an unambiguous representation for all
values .of the parameter 00%. The matrices S l are the only ones which give a
faithful representation. But if we give up the condition of faithfulness for
arbitrary values of the parameters and maintain this restriction only in the
vicinity of the itkmlty w. == 0, it is possible to find other matrices.
~ommerfeld has sho~ in the old quantum theory that internal
quantum nu.!!'Nrsjwhich can be hal/integers" must be introduced in order to
deacribe Certain spectra. It is known that these half integer numbers COLlle
from the spin (cf. 6.2J~ By analogy with (5.3), 'We find for the rotations fi)z
~xp.[~ij~J. e~p.[.i~.l~~]:.:: . . ~ . . )
o
exp (ija>,] I
(S.3a)
It{)1"ATION GROUP
131
withj = 0, i, 1, t ..... All the exponents of the matrix are either integers or
b~lf integers. We shall add to the matrices of odd dimension in whichj is
integer, matrices of even dimension withj = t(2p + 1). But in theJatter, ~ere
is not a onetaone correspondence between the representation of the rotation
group and the abstract elements of this group . When ro. is increased by 21t
the matrix elements in (S.3a.) will reverse their signs because the factor
j = t(2p+ 1) :;.: t+integer
gives rise to a 1 in the matri~ element. To each angle OJ% there are two
corresponding matrices SJ(wz ) and Sj(w;:) in these representations of even
degree. They are twovalued representations. Between the representation
and the group ~3 there exists only a homomorphism. Both matrices 1 and
1 correspond to an angle zero or 21t.
2. Rotation Group and IfwoDimeosional Unitary Group
2.L RELATION BETWEEN THE ROTATION OROLrp AND THE UNITARY
GROUP.
E" Cartan then H. Weyl h.ave shown how to build "a priori" all of these
representations 1 The group ~3 of the rotations around a center is a 3
parameter group.. T\vo of the parameters fix. the direction of the axis, the
thlrd one the rotation angle. Hence we have the problem of constructing a
correspondence between rotations in three dimensions and a unitary three
parameter group_
The Simplest unitary group is the unitary unimodular group '&f z with two
complet variables. The transformations (j of this group can be written
f e' = + prJ
U + t rtf = P*I;+a.*rt,.
(5.4)2
Ct". B. CAltTAN, thesis (1894]: and his papers; 'The projective groups which leave no
plane manifold invariant (irreducibles)"', [1913], and (1914}., See also CAJlTAN [1938].
Cartan& work bas been resumed and completed by another method by H. WEn
[1925} on certain points. These studies are very general and they aim at building all the
possible irreducible linear groups "a priori" and at finding their structure (compare the
footnote on p. J 7 and Appendix IIIj
t A mapping of a two ...dim~nsional complex space on ItMlf can be written as:
1
e' == r:tqiPYi,
r( = y~+~.
F or simplicity 'Are i.t.1I'lpcse the condition that this will be a unimodular tt'(lnSj:?1'matian, i.e.
11
:jI.
ti.o fl,.
L
rhe matrices of the adjoint and inverse trao..cormations a'fe:
..,
:(1;* '1J$\)
(l ~
~./)
\rilli
(Footnote corJilfURd on
tiff!
next pa:?e~)
=:;
132
[eh. 5, 1
The determinant of
(f
is 1; this condition
aa.* + pp. = 1
(S.4a)
which coUPles the real and imaginary parts of a. and fJ and lowers the number
of independent parameters from four to three.
By a stereop,phic projection we establish a correspondence between
every rotation s and a transformation (J of the type (5.4), with certain complex
coefficients ex and p.
Let x, y, z be the coordinates of a point P on the unit sphere:
r+r+z2 == 1. Let x == 0, y = 0, Z = 1 be the coordinates of the
south pole S which we use as center of projection. The plane of projection
will be the equatoriaf ~e and the coordinates of pi, the projection ofP,
wiD be called x' and y (compare Fig. S.l).
I Q order that
(J
be unitary
a == 01
a=
?' =
p.
i.e.
(1
(.~P*
!.).
f5
:=
Ch. S, 2]
ROTATION GROUP
SP'
p ....
SP
13~
e.
1
y'
X'
y == 1+z 
== x 
1+,,
and
p=
XIY
,.
+,,*'
.
1/1+,,*
Y2(1+z)
'
2,*
1+,,2{
1,,
Z=
1+"*
1
or :finally using complex. homogeneous coordinates ~ and ", such that
t = tile with the supplementary condition:
~,. +"". = 1
we obtain
x+iy == 2tt~.,
x == ,,~. + ~,,* t
xiy ==
(5.5)
2,,,
Y ==  i(,,~  ~,,*)
z = ,e",,~
To each pair of numben , and " there corresponds a point on the 1lDit
sphere, since as a result of (5.6), (5.5) is equivalent to x"+r+r  1.
Eve~ unitary transformation leaves (5.5) invariant and coD8eC)uently
transforms a point on the sphere into an other point on the sphere. It ileMY
to see ~t such a tran~formation leaves the anates between two 1iDeI from 0
to two different points C invariant (because the transformation is 1IDitary
and unimodular). Hence the transformation is a rotation.
To each transformation (/ of the type (5.4) there corresponds a rotation
s of ~3' The converse statement is not quite the same for if we change the
sign of and /1: i.e, ~ = ex, P' ==  /1, the signs of ~' and ,,' chango, but
after (5.6) x', J1~, %' remain invariant. Consequently to each rotation s of ~e
group f!}3 there correspond two transformations of the unitary lJnimodular
group ~2: +0' and tl. Since the transformations are linear there corresponds to the product S2S1 of two successive rotations a product (12(11' The
When the point P is on a sphere of radius r :;C I it is sufficient to multiply these formulae by the Teal constant ,." The conclusions do not change.
1
134
c;' = eiCP ,
where
q>
act* =
(Ch. S, 2
Of,
that 2cp
=  OJz ,
00(0 ) =
%
(exp (tiro;;)
0
0.
exp (tICO,)
).
(5.7)
o{wy )
(5.7a)
~~7Y
I
135
I{OTATION GROUP
Ch. 5, 2]
t8)
= {exp (
(5.7b)
The preceding method gives us at once an infinite number of representations of the rotation group, because all the representations of the group fl2
are obviously representations of the group ~3 also. They are easy to construct.
Let us form tensors in the twodimensional unitary space 11. A symmetric
tensor of rank v has v+ 1 components
e,
(5.8)
and 11 we obtain
k=o
en 'il1 li,
(ctef{Jrr)vi( JB*er4Ct*11)i
= L SJ),,,lcttk.
(S.8a)
k=O
efJk"k
,
= 0, 1, 2 ..  v
(S.Sb)
.J(vk)!k!
because if (5.5) is used one finds
~
*
~ qkqk =
k=O
"L...J (ee*),,k(fJ'1*)k
.. :         =
k
(vk)!k!
1 (l!;;*
*)V = mvarlant.
.
,
,S~ +tl'1
vI

(5.9)
136
[Ch. 5,12
The matrices S(u> can be multiplied among themselves, like the m~trices (1.
Then we obtain an infinite number of representations of the rotation group,
each arisin,, from a tensor of order v = 0 1 , 1, 2 ....
The customary notations in quantum mechanics lead us to put v = 2j
and to label these representations by the symbols ~J' j =: 0, iJ 1, i ..
Consequently, their dimension is 2j+ 1. It is convenient to call jk := m.
The variables q of the equation (5.8b) take then the symmetrical form
II
.
q~)
,i+m"Jm
v'(j.+ m)!(j 
(S.8c)
m)!
The group t1IJ 2, from which we started, has as a basis the vectors of the
twodimensional space " 'I, with v = 1 or j = t. These vectors are usually
called spinors. It is the same as the representation D t which is double valued
as we have seen in 2.1. This space is usually called spinorspace.
By taking the real and imaginary parts of the variables " " and the
coefficients a, fJ explicitly into account in order to have 4 real equations
equivalent to (5.4), it is easily proved that if If; ~', ,,', satisfy this system,
they are satisfied also by
e,
X =
A~
X' = A"
+ fl'1*,
+ JUI'. ,
p,~.
+l'l
Y' ==  Jl~/. + AI7'
where .A. and Jl are arbitrary coefficients. In ordel to have XX*+ YY. = 1,
we mU$t put: AAo + J.LJl* = 1.
The above transforma~on, which is very peculiar since it connects X and Y
simulta,neously with and '1 and their conjugates, shows the extent to which t
the baSes of the unitary unimodular group are undetermined.
Intparticular if we put A = 0, p, = 1 we obtain a' pair of variables (,,*,  ~.)
which undergo the same transformation as (" ,,). This can be immediatelyc,
veTified. Consequently after choosing x+iy ==
xiy =
Z =~
as the basis of the rotation group ~3 in the 3dimensionalconfiguration space, these expressions transform respectively as _,.,2" 1 and
i.e. as the three components of the second order tensor in " " or
according to (S.Se) as qf!l, q1 1 ) and (1/ J'i)qb1 ). Thus the group ~3 can:
be identified with the representation D 1
In the same way, the representation D j where j == I is an integer is nothing}
but the representation D, (obtained in section 1) the basis of which are the:
ee*'1"
 e",
2,,,,
2rr'.'
fJ
1, the group
~t,
Ch. 5, 2, 3]
137
INFINITESIMAL TRANSFORMATIONS
(J
Let us put m = 1:0'. The above remark shows that these terms are transformed like
or like q~). Thus the functions Yl m ) are independent
linear combinations of (21+ 1) functions of ~*) '1, fl which, though .not
identical with the q~), transform in the same way. They are the basis of a
linear group which is equivalent to D J' j = I.
These representations are faithful. The others for which j = t(21 + 1) are
double valued.
They are all irreducible and no others exist (this will be proved in note II
which should be read after the following section) .
One final remark: in the space IlJ of the representation gjJ the rotations
O)~ around Oz induce the following transformations, which can immediately
be deduced from (5.7) and (S.8e).
el+m,,'
e,
138
reb. 5,13
axial vector d{J. ;::: (.t) dt lying along the rotation axis. The length of thiJ
vector is eqqAl tQ tJl~ rptation angle dB, dt is an auxiliary parameter (the time
in kinewatics), (J) similar to an angular velocity with components OJ,x, 0)"
co% (ro=:'" = d8 x /dt . .. ). The transformation of the coordinates x, y, z by
tbU {QtatiQn is linear and homogeneous in x, y, z according to the kno'wn
tQrmulae
~
:;:;:
(.(}1~lO%y)dt,
etc.... , x'
(5.10)
( 5.11)
the lp i are supposed to be continuous and differentiable with F:'~fACt to the s;..
The transformations (5.11) form a group when two succe'\sive transformations
,I,
s :x
+
x;
and
T ~ x; ~~ x~ I = lfJ i( x~ . . ~ x~;
t1
t,.)
= TS: X, ~ x;'
U,.),
where the u). are, in the vicinity of zero, continuous and differentiable
(5.12)
The. nature of the continuous group, that is its "multiplication rules n , are
(0 A. ds,
(~lfJi)
.~=1
AS;.,
<!sA
0
Ch. 5, 3 ]
INFINITESIMAL TRANSFORM.A.TIONS
139
as was dt in (5.10),
= '"
'' (OlfJi)

dx,
).
(5.13)
roAds.
AS). 0
The symbol ( )0 means the s)., must be taken as zero in the derivatives.
It often happens, and this is the case for the rotations (5.10), that the
group is not defined by its finite equations (5.11) and (5.12) but by its infinitesimal transformations. The infinitesimal transformations are then defined
by the following equations.
(S.l3a)
'where the (4).,) depend only on the variables x. These functions have of course
to fulfil certain integrability conditions.
Two successive infinitesimal transformations are equivalent to a unique
transformation described by equations which are obtairied in the first order
by replacing a>A. in (S.13a) by the sum (COl + co,). An arbitrary infinitesimal
transformation of a given group is then a linear combination of r basis
transformations with arbitrary coefficients Q).t; each of them is defined by n
functions
(J.)(
(Xi
Xl , Xn ,
= 1, 2, ...' n;
A = 1, 2, ... r.
r is called the commutator of sand T; this operation differs only from the
identity by an infinitesimal transformation. It must IJe a linear combination
140
[Ch. Sf 3
0/
This is the only type of substitution we are interested in. The equations
(5.10) of the infinitesimal rotations are linear and the same thing is by
definition true for any representation of an arbitrary group. Hence we
suppose in (S.13a) that the functions ~A) are linear and we write
dX i =
L
L
(x~)xkw.tds == L ailxk ds
kt 4=1
t
(5.15)
We will put: A == (aile)' A(J.) == X~: and call x the vector with components
Xi and use the conventions of Chapter 1.
dx = A%da;
x' == x+dx
= (1 + Ada)x.
(5.15a)
:=
(1 + Bdt):t'
+
= (1+Ads+8dt+ABdsdt)x
commutator r has the form
+
x'"
r(S,T) = l+Cdsdt,
C :: ASSA,
(5.16)
Ch. 5, 31
INFINITESIMAL TRANSFORMATIONS
141
1)
2)
3)
According to (S.lSa)
amount dl1:
d9~
(1)7
==
d8% == .w.dt,
they displace a vector
de == R# "d8~
d., == R, dB,
with the transformation matrices (cr. 5.10)
0)
0
(
0
R;:= 0 0 1
o 1 0
R, ==
(J)~
== 0
CDs = COx == 0
COx == ro, == 0 .
== co%dt,
dB, == co,dt,
in ordinary space by an
(S.lSb)
0
1
0)
(o
( 0 0 1)
0 0 0
1 0 0
Rz==lOO.
(S.17)
0 0
write
one finds:
C;q
==
R~R,R,R~
:II:
Rs;;
R,RsR.R, ==
R;x
RzRxRxR:e == Ry
(5.17a)
(5.18)
If we put.
we find again the commutation rules (2.20) for angular momenta. The
above calculation is, as a matter of fact only a particular case of the calcula. .
tion in Chapter IT, 3, because (S.lSb) is the expression of (2.19) when the
1/1'. are linear functions of x, y, z.
If one conaiders the , infinitesimal basis transformations A(A), A(p.) ... " (as will be
done later for rotations) one must havo:
1
,.
==
I:
cJ.p., y A(v)
yl
tho cJ..I'." being constants. S. Lie has proved that this condition is suiflcienI in order that
the infinitesimal transformatiotlS considered give rise to a Stoup. The structure of this
group is determined by tho canstants cA,.u, y. These theorems are the basis of Cattan's
work.
142
[eb. 5, 3
= (1 + Rd8)v
unitary vectors
qJ
q;j), a transformation
are the
p.;' : tp'
= (1 + R()d8)cp
(5.19)
. . . , }.
(5. 19a)
(S.18a)
We shall assume these three quantities are the three components of the
angulqr momentum in the quantum state j corresponding to the representation
DJ
Wei justify this definition by the following more precise statement:
A P?ysical system must have a spherical synlmetry in order to admit the
group 9J 3 Hence we are dealing lvith an atom lvith a radial field, i.e . a
mononuclear system. As a result of the Wigner theorem, there corresponds
to each irreducible representation DJ of the rotation. group for such a
system a big square matrix inside tIle matrix H (4.14) i.e. a "system of eigen. .
values" labelled by the indices j an integer or a halfinteger. We will call this
index according to the terminology introduced by Sonunerfeld in 1920, the
internal quanfuln number or better, the angular quanfuln number . and the
states or the atom with such an energy, the qualltulll states j. Each state
Enj is descJ"ibed by the whole set of the (2j + 1) wave functions corresponding
to the representation DJ ..
As for tIle quantities L~, L~), JJI), we are allo\ved to consider them as the
cOlnponents of the total angular momentum of the ,,1.tom: first because they
Ch. 5, 31
143
INFINITESIMAL TRANSFORMATIONS
= i R~j),
M~J) =
R~j),
M~J) =
R~j)
(5.20)
(5.20a)
Hence.forth we shall call these quantities Mfj) the components of the angular
momentum in the state j. The square of these momenta can be written:
(5.21)
3.4 PAULI MATRICES
It remains now to obtain the explicit expression for these matrices belonging to the different representations DJe Let us begin withj = !.
The variables of D i are the complex numbers , and " connected with
x, y, and z by
x+iy = 2'1~*
(5.6)
xiy = 2~,,*
their transfonnation formulas are those of the group c1/2
{1(e' ==
a, +e+
fJ'1
 j3*
arx*+pp
(5.4)
,
a.* "
= 1.
(S.4a)
..)
= 1 + K r 11\.;
{]
j
= Jlf.. IV ..
1(;
= 1.
144
[eb. 5, 13
dIJ
== i WI,
== iv,
(S.22)
:=
2pz, dy == 0, dz ==  2p.x,
i.e. a rotation around the )' axis over an angle dB;, = 2p..
3 Jl = 0, v == 0 .
(S.22b)
dx == Uy,
dy == Ux, dz == 0,
.r.
e
~+)+~t)
::.
(~ ~)
w!) == ~*)~*) == (~ ~)
(5.24)
Cb. S,
I 3]
INFINITESIMAL TRANSFORMATIONS
145
== 2Mz,
M+M_M_M+
M_M:IMsM_
= M_
(5.25)
McM+M+M. = M+,
where we have suppressed the superscript !, since they hold in general1ike
(S.17a) and (2.20).
Let us introduce three infinitesimal parameters, ds, dt, du; then the
transformations arising from M<!), M<!> and ~i) are
MCi)'
~+)
== { de = "ds
d"
=:
= { d, == 0
d'f == edt
M~i) == { d~
d"
(S.24a)
= tedtl
=
i"du.
(5.15)
In order that this transformation be unitary (L'x~ x.
have the following condition fulfilled:
't"'"
dXI
L x, t
i.e.
ds
~ dx~
+ .t.J
Xl ._ == 0
!
ds
146
and
Xl
x,,_
Hence we have
a1k
Of,
fCh. 5, 3
if we put 'A'
aki
= iA
,
al.k
,*
aki
,,,ill
We
calculate the expressions MCj.>, Mf.!}, Jjl~J) and (M(J)2. The coordinates of the space BtJ form the basis for the unitary representation D J
They are the (2j+ 1) monomials q~) of degree 2j in and '1 given by the
formulas (S.8e). We obtain by differentiation
dq~)
J(i+ m)!(j 
m)!
S+ :dq!:'
== J+m,
s_ : dq!!)
'f
J(j+m)~(jm)!
(j
by Af<j>,
s = J(j+m)(jm+l)q~~lds,
m)eJ+m+l,ymldt
.'
= J(jm)(j+m+l)q~J)dt,
J(j+m)!(jm)1
:. dq(}}
S z
m 
..... 
mq(J)du
m
M(j)
<mIM~lml> = <mIM~)+i~j)lml> =
JU+mXi m+ 1)
J(jm)(i+1n+1)
f
<nlfM~J)lm> = m.
(5.26)
These are the fundamental formulas for the components of the angular
momentum. Each of these matrices has in each row and in each column only
one element different from zero. Only the last one is diagonal. III the state j,
the component M~J) can assume the values m, L~j) the values mh with
m = j,jl,c ... , j. In order to separate the different states corresponding
to these different values it is necessary to destroy the spherical symmetry
(Stem and Gerlach experiment).
V'e have according to (5.21), (5.24) and (5.25)
Ch. 5, 3, 4]
147
(S.27a)
If ~ne uses this formula for the state j using (5.26) and the known multiplication rules one finds that the matrix (M<j)2 is diagonal and has the
value:
(M(j)!,m = (i+m)(jm+l)m+m 2 = j(j+l).
(5.27)
say
of
and
148
[eh. 5, 4
and, aocordins to the Wigner theorem, each of the levels En) is split in such
a field into (2) + 1) discrete levels.
From this
the reduction of D J follows at once. All the matrices of this
,
aroup reptesenting fetations Q)% around the z axis are in the diagonal form
(5.3&). As a result of the perturbation A. W they will be divided into (2j + 1)
one dimensional matrices without any change in the matrix elements and at
the same time the eigenfunctions are supplemented by terms of the order of A..
Under a rotation 0). these eigenfunctions undergo the following transformations:
"':,. II:
m == j, j 1, ...  j.
(5.28)
+J
Wo "'". ==
w".""
t/Im'
.'   J
lfwe carry out a rotation 00. we have, according to the invariance properties
of Wo " and' the transformation formulas (S.28),
Wot/l ... exp (imQ}.) ==
This relation can only be satisfied for all the values of the angle
00.
if
E,,)m == E.J+Aw
This formula embodies all the information which can be obtained by
group theory. The perturbing function and consequently the value of the
Ch. S, 4, S]
149
constants w". depend on the way in which the field influences the atom. For
the first attempt we will try to apply the classical formulas of the Lorentz
electromagbetic theory to the BohrSommerfeld atom model: i.e. to the
angular momentum L z of the electrons of the atom around the z axis there
corresponds a magnetic moment (i.e. its projection on the z axis)
(5.29)
and an energy
lW = HvII%
H
 L%
2ntoc
where mo is the mass of the electron, e its charge, c the velocity of light
(H plays the role of l). Since L% is in diagonal form JI. and Ware also in
diagonal form, i.e. to each element mit of the matrix L:z there corresponds an
element of the matrix A. W
(5.30)
is the Larmor precession frequency.
The experiments did not verify this formula. To include the anomalous
Zeeman effect, the second member of (5.30) must be multiplied~by a certain
number g, the Lande factor which changes value from one spectrum to
another. The simple Bohr model which would hardly have explained the
fractional numbers j, must be modified. This statement is the origin of the
theory of spin.
B~fore treating this problem it is necessary to come back to the theory of
angUtar momentum and to establish their quantum addition formulas. In
this way the classical vector model of the atom will be completely justified
and perfected.
COL
Let us first consider the problem from a physical point of view: suppose
one adds the last electron to a monovalent positive ion in order to form an
atom. The state of the ion is known. First we neglect perturbations, i.e. we
suppose that the action of the ion on the electron is described by a central
field. The electron forms a second system in a state that is easily defined and
150
[eb. 5, ~
calculated by the Scbrodinger theory. Then the ion and the electron are
further coupled by taking a certain perturbing function into account. The
problew is to find the state of the complete atom formed in this way_ That is
what levels may result from a certain initial level as a result of this coupling.
A detailed dynamical discussion will not be undertaken here; this discussion
would be difficult and in fact has been done only in some simple cases.
We shall only give a preliminary purely kinematical study leading to a
classification of the energy levels.
Two groups are essential here: tIle rotation group and the permutatioft
group. Only the first one is actually of interest to us but the method is
general. We couple two systems with a spherical symmetry whose angular
momenta are res~tively il andj2 and we look for the angular momentumj
of the total system submitted to a coupling with spherical symmetry_ A
similar problem arises concerning the spin and orbit.aI momentum.
S.2. PRODUcr OF TWO REPRP..sENTATIONS
Two systems for which the Hamiltonian is invariant tlnder the operations
of a group (I are brought together. Their interactions are supposed to allow
~C) same group. They are respectively in the quantum states correspondin.g
to;,the irreducible representations ~1 and ~2 of <!J (cf. (4.13) and (4.14)).
How can the resulting states of the total system be classified?
.According to our hypothesis on the interactions this classification is
i1irJqe1llltmt of their magnitude; this classification depends only on the represdntatioD of G in the function space and can be found in the limiting case
~here the dynamical coupling is infinitely small (but different. from zero).
. rhe gradual strengthening of the coupling alters the positions of the levels
themselves without any change in their distribution over levelsystems and
their degeneracy.
Let Xl' X 2, " ., ..'%7., be the coordinates of the particles of the first system,
Y1, Y2' ~ ... , y" those of the second systerrt, n1. an.d n2 the dimensions of the
representations l 1 and { 2 t I.e. the degeneracy of the corresponding levels.
'fh:~ first system is in tile energy level El t , the eigenfunctions of which are
arbitrary.. linear orthogonal
 , combinations of 11. basis functions, Le.
l
'" =
"1
m~l
The "components" q", are the variables of the' representation I t and the'
t/lm the basic vectors of the sp~Jce ~f"
Ch. 5, S J
151
In the same way the second system is in the energy level 2' the eigen
lp
1&1
The q~ are the variables of the representation ff2' the CfJp are the basis
vectors of 812
It is known that if the coupling is loose the SchrOdinger equation is nearly
separable in two independent equations, the eigenfunctions of which differ
little from the zeroth approximation eigenfunctions tp = t/llp i.e. linear
basis functions 'P.JI. == l/I".tpp.. The perturbed
combinations of the
levels differ little from the level E = El + E2 the degeneracy of which is
nl n2 for coupling of strength zero. All these results are well known. We have:
"1"2
'1'
:=c
~JJ'
t/lcp .. L,
q", qp. "'m lP"
"',.
:: ~
~ Q",,, 'I'm".
( 5.31)
1ft.. "
Bl2
tll1
(5.32)
and al 2 and its coordinates are
(5.31a)
r
i.e. all ~ossible products of the coordinates of ut1 and 1l2 .. This is equivalent
to builtling a tenaor of the second rank/rom two vectors. (Compare Chapter 1~
1.2)~
(5.32a)
From
111
r
"2
one gets:
pal
CfJ,7pp
152
'l!
+ S tp
[eh. 5,
= L: Qml'S 'P
mp.
L: Q;pWrp
rp
with
"1112
Q;p =
{5.33}
1'=
= ,(Crm,PI')'
C1
= (Crrn ),
C2
= (YPJl).
(5.33a)
If 'lJ 1 and l{} 2 are two representations of C!J, ttl is also a representation
of C. This can be easily verified. But generally this representation is not
irreducible even if f!ll and '62 are.
Conse,quently, if we want to use the Wigner theorem and determine in how
many distinct levels E will be separated under the influence of the interaction
between the two systems and what will be the degeneracy of each of these
levels, the reduction has to be performed further. Our physical problem is
then t~1ated into a purely mathematical problem: .How to ,educe the
product t6 == 'lJ 1 X ~2 in its irteducible components. To each irreducible
compon:ent, that is to each invariant subspace of fJl 1 X 81 2 , there corresponds
a level whose degeneracy is equal to the dimensions of this invariant subspace.
~.3.
Thel problem which has just been formulated is easily solved in the. caso
of ~ unitary unimodular group tfl2' or what amounts to the same .in'th6
of therotation .&roup ffl 1 From these one. can obtain the ~. for:
rePresentations ~f higher dimensions. The reduction formula finally arrived
ca
(5.34)
First let us consider rotations CDs around Oz. The matrices SJ(J)z)~ and
Sr(OJz ) are diagonal and have.tIJo form (S.3a): one of them contains the
elements exp ( im wz ) with m j~j 1, ... ,  j; the other one the elements
exp( im'wz ) with m' . j', .. _, j'. To the operation ())% there corresponck
in the product DJXDjl a matrix wbiclt remaIns diagonal after (5.33) and t~
elements ofwbich are the (2}+ 1)(~' + 1) exponentials: expi(m+m')ro:r;' =
em+m'(e = exp(iro~) among these [2U+j')+1] only are distinct .
Ch. 5, 5]
153
j+j'l
il+j/l
j2j'+j'
"
. . . . . . . . ..
j'+j'
...
~.
jfj'l
j+j'2
i+j'2
. .,
j.1' I
....
i"
. .. i J
}]
]I
. . . . . . . . . . I . . .. ......
U2j'+j/)
(j2+j')
Ul+i'l)
(jl+j')
(j+j')
U+j'l)
::::::::::: I::::
~.~:!~ :.~). :::: I
.=
i+j'
 ( }. )")
(jj')
'" . . . . . . . .. ."... I
,0,
( ]t)

2)
 (i+j' 1)
(j+j/)
We will be satisfied here with this hint Wllich is not a proof. It mainly
serves to illustrate that the number of basis functions is sufficient to obtain
(S.34}.1
The formula (5.34) is equivalent to
DjXDjl
= Dj+j,+DjiXDj,_t
(5.34a)
To establish this equation rigorously the space iRJ x ItJ , must be decompose~ in an irreducible subspace IlJ +j , which corresponds to the representatio"n D j +J, and one other reducible subspace IlJiXUlJ'ie This decomposition can be obtained by looking for the basis vectors of Dti+jl (cf.
Appendix III).
The formula (5.34) is the symbolic translation of the addition rules of
angular momenta into representation theory language. According to H.
Weyl it is the fundamental formula of the classification of atomic spectra
as well as of the theory of chemical valency.
5.4. TOTAL ANGULAR MOMENTUM
Let us come back to our example: we bring an electron and an ion together,
t\VO systems both of which have spherical symmetry_ One of them is in state
1
This can be completed. using the theorems about the chrtracters (Chapter 3, 11.2).
154
[eh. S, '
t?,
dQ(mm ' )
=
L M mm ,; mtm
'1
Q(ml' m;)d8.
ml,"' 1
I.e.
(5.35)
Or using the notation defined by (S.33a)
(5.35a)
to
an
'f' .'1'
Here the integer I plays the role of j and the values I =: 0, ], 2 .. ~ corre..
spond to the so. .called s, p, d~ .. " states of the eleetron. In the zeroth approx
Cb. S, S J
155
imation, i.e. when one neglects the interactions between the electrons, the
wave functions of the total system are linear combinations of the products
"'~f) t/I~~:) the coefficients of which are the variables of the representation
D,XD . The levels E := E",+En'I' depend neither on m nor on m'.
If we" take into account the Coulomb interaction between the electrons
the representation D, X D must be reduced in its irreducible components
as in the formula (5.34). To" each of its components there corresponds a level
Ea'L and an angular momentum operator M(L) (where L .. 1+ I', I + l' 1 ...
111'1) i.e. a welldefined state of the atom, L is the total azimuthal or orbital
I[tID1Ztum number.
156
[eb. 5, IE
For each ele.tron the Schrodinger theory uses only three quantum numbers n, I, and m (cf. 1). On the other hand, the study of the anomalous
Zeeman effect has led us to consider halfintegers j which playa role similar
to the numl1er I and which correspond to the representations of the group
3 of even dimension. Then it is necessary to consider a fourth quantUDl
number in order to complete the hypotheses of wave mechanics and to set
up a connection between 1 and
j"
"
Let us consider as Sommerfeld did the experimental results concerning
the spectra of alkali metals. We have just seen at the end of the preceding
section that these atoms have completely filled shells for which j is zero,
plus a single external electron the state of which is defined by the total
quantum number n and the orbital quantum number I playing here the
role ofj'. In this case the formula (5.34) shows that the levels resulting from
th~ coupling must be simple. The experiments, however, show that they are
double. The two states of this doublet are distinguished by a fourth quantum
number and this number can only assume two distinct values. We foresee:
that these values will probably not be integers because the Zeeman effect!
for the alkali metals is anomalous in a magnetic field; the spectral terms arel
divided in an even number of components (2j+ 1) so thatj is ahalf...integer,l
The *umbers I are known from the study of spectral series and selectionl
ru1es~ The experiments show thatj is always equal to I+!.
Consequently the two states of the electron which form the doublet must!
be ,distinguished by the quantum number s = +t with j = I+s.
.
In the more complex spectra involving many electrons such as the alkaline~
earths, these hypotheses and the vector model were able to give an explanal'
tion of the experimental facts. This work was done by Sommerfeld (192()..~
1923).
;
As a result of a precise discussion of empirical results Lande discovered mt
1923 a remarkable relation between the splitting factor 9 and the numbenl
J, L, and S which replace j, I and s in atoms with many electrons. TbPI
relation can be written, in the case of alkali metals
i
_ 2j+l
g  21+1
( 5.36)
Cb. 5, 6]
157
until 1925. However, that time Uhlenbeck and Goudsmit had the idea to
connect these facts to some phenomena of a very different kind: the gyromagnetic effect, and thereby found the key to the problem.
Einstein and De Haas have measured the change in angular momentum
of a ferromagnetic substance when the magnitization is suddenly reversed. 1
Barnett studied the inverse effect where a certain magnetization is created
by rotation. These experiments which were improved more and more
showed that the formula (5.29) connecting the angular momentum L z of the
atom to its magnetic moment Jt % (which comes theoretically from the existence of the electron orbits) is not true for the elementary moments of the
ferromagnetic materials. For these substances the righthand side of this
equation must be multiplied by the factor 9 = 2
(S.29a)
It is sufficient to substitute in equation (5.36) I = 0, j = t in order to
obtain this factor. 2
All these facts suggest the following hypotheses which we can express as
follows by using the vector model:
The quantum number 9 is related to a fourth and last degree of freedom of
the electron which can only be a rotational degree of freedom. The electron
then has ~ angular momentum or spin, the projection of which on a given
axis Oz Can only assume the values
(5.37)
The corresponding magnetic moment is given by (5.29a). Hence we have:
en
Jt=+z

(5.37a)
2moc
according to (5.29) and (5.26) this moment is equal to the magnetic moment
of a porbit (/ = m = I) i.e. a Bohr magneton. 3 The ratio of the magnetic
1 A similar effect can easily be observed when a gyroscope is suddenly turned over .
s'In experiments SUCKSMITH [1930] succeeded in measuring the Lande factor g for
certain paramagnetic ions directly by gyromagnetic experiments and he found a value
equal to the spectroscopic number.
8 According to tho correspondence principle one .finds in classical elcctromasnetic
theory the formula (S.29) for an electric charge moving along an orbit. The formula
(5.29a) for a spinning electrically charged sphere correspOnds to considerations in the
theory of Relativity (compare for instance M0LLER [1952]).
158
[Ch S, 6
as for the
orbital motion.
As the ener.gy difference between the components of doublets and multipleu:,
is always smalI the secular equation of Schr<Sdinger is a good first approximation and the dynamical interactions of the spin (interaction with the
orbit or with the spin of an other electron) can be considered as perturbations. 1
6.2. TRANSLATION IN QUANTUM THBORY (PAUll)
Let us consider a system with only one electron: the Schradinger wave
function y,(x, y, z) must be replaced by a function of four variables l/I(x",
z, s) where s can only assume the values !.
If we know exactly how the spin is oriented (for this we must use an
external magnetic field to define a certain direction Oz of the space as in the
Stern and Gerlach experiments) we can fix the value of s. If spherical symmetry is preserved, which is usually the case, two values of s are possible, each
one with a certain probability. It is necessary to use two functions at the
same time,
I/!l(X) == t/I(x, y, z,
"'1
=c
t/I(x, y, z,
t)
where y,! d't and l/I; tfi2dr represent the respective probabilities. for the
two values of a in the elementary volume dt
dxdydz. These two functioDl
can be cPnsidered as the two components of a vector in a twodimensional
space _~ or spinspace. This vector is sometimes called a spinor. The state of
an atomjc system with one electron is then represented by a twodimensional
vector "or spinor:
(5.38)
"2
and
are t\VO orthogonal unit vectors; to each of them there corresponds a welldefined state of spin orientation: they are pure spin ju;nctio1l8.
Their orthogonality means that an electron cannot at the same time be in
the two states of spin +; and 1=
U1
+t) == 0;
Ut( t)U2( !)+Ut( +t)U2( +1)
Ut(
1) == 0,
U2(
o.
Ch. S. 6]
159
two spaces and of the direct product of two represea~tion8 we see that
tlte space of the junctions y, i.e. the total/unction ;"cludingtlJe spin U:11te
product lpaee II. X \Jl. This is exactly expressed by the formula (S.38} and
this is ~ starting point for the theory of the spin.
It DOW remains to establish by some hypothesis how the. vectors of the
space 81, behave under a rotation of the system. We shall assume that
rotations in ordinary space induce in the space fJl~ transformations which
form an irreducible representation DJ of the group Is.
This assumption seems so natural that it is difficult to make a di1fQrent
one. In fact since It. is a twodimensional space an>d if the represen~tion DJ
were reducibl~ it could be deco~pOsed in two onedimensional representatioDs which would not tell us anything.
Since the space IlJ which corresponds to D j is (2j+ l)dUneDsio~ j must
be equal to 1 and the group ~3 induces in the space It. X \Jt the representa
tion DtxD.
6.3. APPLICATIONS
Di.'XD,
:=t
L D J == D,+t+D,t*
(5.39)
(5.39b)
The momentum M is the sum of the orbital momentum M<l) and thC
spin momentum Mii). The first can be defined by (2.18) (apart from a
factor Ii) but the definition of the second one can be given only with the
more or less explicit help of the theory of the rotation group.
160
[Ch. S, 6
3'0 The components of the spin momentum MCt) along the three axes are
given ~y the Pauli formulas. Only M~i) is in a diagonal form with eigenvalues :hi. These are the two observable values of the spin momentum
projected on a fixed direction of the space Oz. Whenever the last one is
determined then ~i) and M~*) cannot be determined simultaneously
because they are nondiagonal matrices.
6.4. COMPLEX ATOMS
~3:
....
l/The 'Wave functions tpl~d fIJI of (5.38) can be calculated in the zero~ approximation
by scalV~hr6d.inaer th.eC>rY and they will have the form (~.l) aftet at ~Qvonient normalization. Consequently in an atom with r electrons tp can be written 'in tbe same approxi.
matio~ as
(a)
1p\.Xl' ., Sf'
) _
'PI
',1 ... 1
(I)
U,
Cr'
where the upper indices label the. electrons. The indices i, k, I . can only assume the values
1 and 2 corresponding respectively to
and $ = t.
If'there are interactions between the electrons the product of individual space functions
is ~.,.~ b~ a ~in"e 'function and we havo
8==
(b)
+i
'
u,(r).
If the perturbatioDi from the SPin are small tp,~ . , can in principle be calculated by the
scalar theory (with only the Coulomb interactions).
Ch_ S, 6J
161
'2
L DL
This operation gives one term for each possible Lvalue: L is the total orbital
quantum number; to the values L = 0, 1,2, .. correspond the states S,
P, D. .. of the atom.
Then one reduces
DjXDtX XDi
==
I: Ds
= Dl+Do
D.XDiXDi
= Dl XOt+DO)(Pi
= llt+Di+P.i
(S.~)
(~.41);
... ':,~
162
[Cbs S, t 6, 7
coupling in. which the coupling of the spin of each electron with itl own ,orbit
is more important and gives a resulting angular momentum j; the momenta J
of the different orbits are coupled according to the equation
DJI XDJ2X ..
XD J,.
= L DJ
7 Selection Rules
to
two
Jl. +
==
fJJC +iJJ, ,
J.l
=:
JJ~  ip,
and JJ:
~o ~f ~ s~~~
Il..pm
==JIm'
L Y,F.,(P+)J'''''I J== .;
J.l~ "'WI
= .
(5.42)
H
For example each of the constants, (p.~)J"'.J'm" raised to the second power
is proportional to the transition probability from the state Jm to the state
j'm' and to the intensity of the corresponding spectral line (with a polarization alona Oz). Without magnetic fields the levels are independent of m
hence tlUSindex caa be suppressed and one can investigate the selection rules
for transitions j ... j' only.
We will no&lect here, as in Chapter 2. 6, the radiation of higher order muttipotes
(quad!upolfjs. etc..)
1
SELECTION RULES
Ch.. 5. 7]
163
are constants, is a sum of terms which transform like the components of the
vectors belonging to the spaces DlJ" i.e. according to Df, .... , with)' == i,
1, i. ..
Since both sides must transform in the same way under the rotation S,
we find that all the terms of the righthand side must be zero except those for
which i' a=)+ I, j, or }1.
Hence we have the following selection rule (the arrow shows the possible
transitions)
(5.43)
j+jl, i, j+l.
In case) = 0 we have, however, D1 XDo s= D 1 ; the only possible transition is j r:.:: 0 . j == 1, i.ell 0 + 0 is forbidden.
One ~nds by the same method the selection rules concerning the transitions of lthc magnetic number m in a magnetic field. The operations of the
group 91 2 i.e. the rotations. around Oz through an arbitrary angle co are
the onlY allowed operations: p+ is then multiplied by exp (ico), l/I}", by
exp ( ....jjmw), "'J'm~ by exp (  im' Q. 1
For a totation with an arbitrary 0) one has
p+ "'Ja exp
(iw(ml) =
J'm'
AU the terms of the sum in the right. .hand side are zero except those for which
m' = ml. By a similar argument for IJ and Jl6 one obtains final)y tho
following selection rule: the only allowed transitions are~
", +
ntl, m, In+ 1.
(5.44)
The first and the last one give circularly polarized light in the xy plane with
two opposite directions of rotation. The transition m + m gives linearly
polarized light with a polarization plane parallel to the zaxis.
1
For the
(S~3)~
164
[Cb. 5, 8
..
The group of pure rotations is not the only one that is implied by the
spherical symmetry of atoms. This symmetry is also preserved under
refiections, which are all the products of rotations and the only operation
connected with "symmetry with respect to a center", i.e. inversion of the
axes:
X
= x y
y z
z.
= E.
The group ~3 is extended by this operation, which commutes with all the
rotations, to a' group !;. As a result of the preceding equation this inversion operation will have representations in the form of a diagonal matrix
containing either + 1 or  1. The eigenfunctions or basis vectors are multiplied by the factor b = 1 as a result of this operation. This factor b is
called the parity I, signature or reflection character of the representation.
The.. parityof a wave function "'(Xl, Yl' Zl, X2, ; 91,32' . ) depends only
on; the space coordinates of the electrons and not on their spin s. The spin
can be considered as an axial vector (.gular momentum, magnetic moment)
the 90~nents of which remain invariant under inversion of the coordi~te
axes. ~e operation" does not operate on the vectors of the space'It.. ,
but dobs
OD the vectors of the space It.
f '
In the one electron problems the orbital wave functions (." 1 and "'2 in
(5.3~J) are as a result of (S.l) homogeneous polynomials of degree I in x, y
andl z, 1 being the orbital quantum number, hence they are multiplied by
( 1)' by inversion of the axes. The spectral terms have then alternatively
the refteCtion characters b = + 1 and 0 = 1, i.e. they are positive or even,
negative or odd in the following order: s+, p_, d+ ,1 ... which is the most
frequent order even in very complex atoms. This order is characteristic of
those terms which are called normal by the spectroscopist~.
The parity of the states of an atom with f electrons can be calculated
a prlDri whenever one can give to each electron a welldetermined orbital
quantum number I, particularly in the case of RussellSaunders coupling.
Recent developments in the theory of elementary particle interactions again foc~
att~tion on the subject of parity. For thiS development
refer to the literature quoted by
La P960] .. A group theoretical classification was given by MELVJN [1960].
1
we
Ch. 5, 18]
165
"'2 .;,
(5.45)
A perturbation will arise from the coupling of the electroDi; this perturbation can be important, nevertheless it always preserves the spherical
symmetry of the atom and changes neither the representations of the
group ~3 nor the parity ~ The value of b is unchanged according
to (5.45).
In the helium atom the first electron is generally in the state 8(1 0) and
is completely determined by the quantum number 1 == L of the second
electron: the terms are normal.
This is not generally true. For example let us consider the. atoms COntaiDjDI
two electrons in their nonfilled shell! and let us suppose that both are iD a p
state (/ == 1). The formula D1 XD. =: Do+Dl +D2 shows that three
kinds of states may occur: the S statea(L =: 0), P~8"~(L  1) or D states
(L = 2). These three kinds of states are known in Alg; they are tile socalled
primed tenD.$ and they all have the same parity
8 == (_1)'1+'2  (1:f = 1.
The experimental importance of the parity lJ is shown by a seteoeiDa rule
discovc?red empirically by Laporte, Itullell md Sa1lDden.
The ~sn of the comPOneDts of the electric ~ II .........0 every:
polar ..ector are
UDder invenion of _ : the ro..... iadaceiD!
ordituaryspaoethe traDaformatiollloftheJrGUP
with the l*ity 8  I.
Let us come back to the equations 5.42 and replace the ia.dicelj and", by;
11' 12 , I if the IY*B' U1ldergocs the operation x: tbe~. of P, is
~ .... ~.. ...
18 ."",....t'tipJied by 8 _ (_1)" +la+ +'1  ... ~J,
In.
C;11&1.1.""",
" , . " 11
.......U1
.uv ifJ'l'lr:a "1 uz
~ == (1)"1 +"2+ +1'1. Since the matrix elements (P+)" .. I't_. _1'/ are
constants it is necessary that
cha."
1
f.
't.
8' ==
~.
(5.46)
rule of Laporte).
The completely filled shells do not cootrjbute to the total orbital munber L. This is a
consequence of the Pauli principle.
1
166
reb. S 8,9
The selection rules for the numbers Land S as well as those of j can be
obtained by considering the rotation group, but they are only approximate.
The operator of the electric moment p. + , Jl , 1'. changes only the orbital part
of the wave functions (1/1 ilc " in the formula (a) page 160 footnote) without
any action onth.e pure spin functions (u~ 1 ) u12 ) .... ). As long as the perturbations
resulting from the spin are weak and the distance between the components
of the multiplets is small, these functions t/I can be calculated by the scalar
SchrOdinger theory and they haye an exact total quantum number L and the
spin functions have an exact total quantum number S. Hence when one writes
the expansions (5.42) of the components of the electric moment the pure
spin functions are the same in both members ofeach equation and the expansions
01 the second members. can only be done in terms oj" space eigenfunctions
"'ft .... '. An argument identical to that of the above section leads to the
rules!
+
L+ 1,
L~
Ll
or AL = 0,
1 S + S or AS = O. (5.47)
sInce the
.:
Ch '):7
<
Jt. .... )
~;
Sl'ARK E;FFECr
'::J
From th~, ,group t11eoretieal point of view the essential difference bet\veen
these t,vo pnenomena COJnes frorn the different symmetries of the magnetic
a.nd electric fields~ The first one has the symmetry of a rotating cylinder, it
admjts only the Abelian group formed by the rotations !!tJ1 aronnd the~field
and a reflection \vith respect to a plane perpendicular to the field~ 'Tht' second
one h.as the synlrnetry of a cone of revolution whickl al1o"~vs the' iO!f.. Abelian
group ,g{:; of fntations and refleGljons~ tJbvio"Csl:;,v ;;:4? is a subgroup of ~}~ .
If there is a degenerate level corresponding to the irreducible representation
!!tj of the group '@.3' a nlagnetic field will split the level into 2j + 1 cOlnpo'"
nents (In :.~. j,j ..l" . ~ . ~ ._j) according to Chapter 4, 3.2 and 4 . The splitting
in an electric field will be less conlplete. 'rhe two values ~ 1'1'1 of t!le tUagnellc
quantum number (ofvve could say the electric quantum (i1.uuher Iml)
correspond to a unique level which cannot be split by the electric perturbation (essential degeneracy). Only the level m = 0 contains i\\'o ternls} one
posi tive~ th.e other negative with the parity ,+ 1 and  J. (cf.. 4). A~Jtogetltel'
the splitting by Stark t~ffect will consist of j+ 1 separate levels"
(yenerally thisdecorflposition is of second order except for an accidental
degeneracy (hydrogen ca~e), the expansjon of the perturbation. begins
terms proportinnal tr; the S(H~are of' the .field .
fUllction is
....1..
where ,'% is the field and Ji,z. = Leizi is the projection of the electric m()ment on this field. l<he diagonal elements of tIle perturbation rnatrix are
",",,.,,1,.
1
t S f~1',
q (.1~I (J)
.1 (J)')
'. 0 ..~....
'',10 .... H 't'l...,. .;.(J)
th
 e S(c.d.aI
pJ. Ouuc
M ' flz t.//.\l;
Wlh;
uC h are a.;.11 Ze!
ttt..("3.1J:.ii.
~,,\.! ~ He ,) ~i
have the sam.e parity for a given J and the total result 1~: antisynlmt!tric
due to the odd parity of the operator J.l:z.1
TIle selection rules (5.43) and (5~44) remain exact but (5.47) are violated
as soon as tbe electric tieid is strong enough to create eigenfunctions differing
fronl thelT zeroth approK~mation. by a significant amoullt .. i.(~. they start ti)
sho\v the symuletry of the new problem. 'The rule of Laporte is unnl0dified
by a magnetic field which is represented by an axial vector and hence gives
no change in parity. This rule is, however, not verified in a strong electric
field (a polar vector) since the perturbed wave function does not have the
''I"'
168
[eb. S, 9
Let US come back to the expansions (5.42) of the components of the electrio moment. Tho lefthand sides of these formulas are the products of the
components of two vectors. The first are p+ , p._ and p.. which transform under
a rotation as x+iy, xiy, Z, i.e. as the basis variables of the representation
1
9 1 or more precisely (cr. 2) as q~11,
) and 2 t q~l). The second arp the
functions ';Jm which transform as the set q:.f> wit4 m = j, ... , j. At the
righthand side the constants JlJ'.' t J"", which will be written with a clump of
q1
the indices as (P)JAI,jnt, are multiplied by the fUDctions y,1M which transform
as the basis variables of the representations D1  .
The equations (5.42) are essentially the same as relati011 (S.A26) in Appendix III~ provided we substitute in this last one j' ::Ill 1, m,' =: 1, 0, 1,
J =)+ 1, j,/jI, m+m' == M == m+ 1, m, ml. Referring to the remark
following the equation (S.A26) the matrix elements (p.+)J.JJI, (p,)P..IJI
and 2*(p,S)Jm,JM have the form PJC~ where the coefficients C are given by
Table S.A.l in Appendix III, the PJ remaining arbitrary. This is the first illus
to
=:
i+l,
(P+)IfI,ml
(Jl)".. _+1
(p,)., ",
for j
+
J = j,
(Jl+)".,ml
= PJ~(j+mXjm+i)
(P)".,m+l
= PJ.JUm)(j+m+l)
CU%).,m
for j
+
J == i1,
= PJ+fJ(jm+1Xim+2)
== PJ+ IJ() + m + 1)(J+m+2)
== PJ + 1 J(j+ m + 1)(j + m + 1)
(5.48).
....
= p)m
(Jl+)",.ml == PJl~/(j+mXj+ml)
(p)... JIJ+l := PJ 1Jlj m Xj:"'=i)
(p..)".,1fI = fJJl J(j+ m)(j m).
All the other matrix elements are zero. Hence we found more precisely
the selection rules concerning} and m.
,
These relations have been checked experimentally in vieak fields. We notice
169
STARK RPFEcr
Ch. 5, 9]
that the components of the j + j transition are of exactly the same form as
the components Me.{!, M!! and ~J) of the angular momentum in the
state J (section 3.4). This is not surprising.. In both cases the axial or polar
character of the HelOT does Dot make ~y difference in the pure" rota~ions.
For the same reason the formulas (5.48) are valid in Stark effect as well as
.,
to
(5.49)
M(8)
and
M(L)
in
the parts of the space It where these do not operate. The above equation
can be decomposed in three equations of the same form if we use M + , M 
and M .
As ,,'e saw in section 6<'the angular momentum due to the spin must be
counted twice in the calculation of the total magnetic moment. To the vector
M corres~nds a magnetic moment .A and its projection on the field H
can be written as a result of ~S.29) flDd (5.29a) as
(ft
:=
;II:
P[M~S)X(I)+M%)
(5.50)
170
the assumption that the total magnetic moment is the sum of two vectors
PAf(l.) and 2j)"W,:sl.
1o. At 1irst let us suppose that the field is weak with regard to the spin
orbit coupling (L S) which we suppose to be of the RussellSaunders type.
The energy differences of the Zeeman components are small with respect to
the splltting anlung tIle different components of the multiplet, which wjll be
split separately.. The spherical syrrtmetry of the atom is hardly modified.
If one makes a &uitable choice for axes, the space Dis X DlL will be reduced
to subspaces 8lJ irreducible with regard to lj)3. The operator M of (5.49) is
decomposed into a. sum of operators M(J), each operating on one of the
subspaces UlJ and each being an infinitesimal operator of the different
representations g; J" rrhus
M
~=
I: l~,,(J) =
[}\f(S)
XI
+I
M(L)],
::: 
P1I[M~S) X 1+
L M~J)].
(5.51)
The SI)litting of a terrrl .1 is, in tIle iirst order ~ obtained by considering only
that part of the operator, or that part of tJle correspo nding matrix,. which is
related to the space fft J That is only the part related to the (U + 1) basis
func1jons of the representation D J is considered:
(5.52)
\Ve kno\v the operator 1"17: which has. been calculated in 4 . It is defined
in;the space of total anguJar momentum. by the equation
+J'
Mzt#Jm
12 m'=12
J'
311d 'l;NC
tfrJ'm,(M~)!;~
J'
and these
t~'()
Ch. 5, 9 )
171
STARK EFFECT'
/ttl + and M _, have the form (S.A26) in Appendix III ("vhere one has to take
j = J, jf = ),' ,T = I') m + m' = m').1. Then Sz =
S~J). lChe lIlatrix elements
(M~J and (~~J are proportional to the constants C:"ltl' i.e . proportional to
each other \vhere the constant of prc,portiollality P.; is independent of m and
is the same for S~,J) and S~J):
2:
S~J)
= PJM~J)
(5.53)
== pJ(rn).
Finally we obtain
(5.53a)
a similar forlnula to that of section 4 but with a coefficient g == 1 + PJ \vb.ich
is called th.e Lande splitting factor: the energy difference between the Zeeman
com.ponents is g times the normal differences.
This factor can be very simply calculated as follo\\'s: Let us consider the
part of the operators fri operating in the space _(J) and let us put
(I X l\tjL)(J) =
t J ).
S(J)
+ 15J )
or
.en ==
lYl(J) 
stl )
which expresses the addition rules of the vector model. This equation shows
that (J), 8(/) and L(/) commute among themselves since S<J) and
operate
on dMerent spaces . (Spin space and the space of the functions tJ!(x).} Hence
.n/)
vie
can "~vrite
.. S(J),
or according to (5.53)
2M(J) S(J) = 2PJ(M(J2 = 2p.1 J (J + 1)
= J(J t1)4 S(S + 1) L(L+ 1)~
and finally
9 = l+PJ = 1+ J(J+l)+S(S+1)L{L+1).
(5.54)
2J(J +1)
FOl'the geometrical meaning of Land~ g . . factor see Mayer B.nd Mayer p. 344 6g.15.2.
172
[eh. S
AW == pH(mL+2mS)
pH(m), mL
L, Ll, ... L
ms == S, S1, .... S,
aD
the eneray differences between the split levels become normal again: as
they are large with regard to the energy difference between the multiplet
components and as the selection rules remain valid, the field gives rise to a
normal triplet. It is the PaschenBack effect.
The intermediate cases can be studied without difficulty.
Appendix I
THE CONNECTION BBTWBBN A FOR.MAL SBT OF BASIS FUNCTIONS AND
THE SPHERICAL HAIlMONICS
Becauso we have used a formal choice of basis functions, the qf", we must
now consider how to deal with actual physical quantities. It was mentioned,
particularly in 2 and Appendix III, that the results obtained for the represe~tations
are independent of the basis. Specifically some of the " 17
,
co~ be replaced by 1]* and thus simplifying the basis functions to mo. .
nonfiats. As a result we do not have a onetoone correspondence between ~,
f/ and x, y, z anymore. It is necessary to consider the inverse process. That
is if there is a set of normalized monomials
rI+ l8 as in (5.80) and if j
il"an intesert what is the corresponding description in x, y and z:J
The connection between the ordinary variables x, y and z and the formal
variables ~, " are given by the following set of formulas:
,*
,iIn
x+iy == 2P1~
xiy ==
Z
I"V
+'12
2~". ~
,2
== CC*",,*
JIv
(S.AI)
+C'1
The first part of the equation. express the original results obtained in 2.
The seco~d part indicated by" ,...," shows the way these quantities transform.
Solving this for the separate variables the equations become, ."
(S.A2)
APPENDIX
Ch. 5]
173
Using the fact that these three quantities transform in the same way
consider a scalar defined by the internal product
,>
:z
,1,,2
x  +y 
~2:2
z~".
(S.A3)
K == (x+iy),,2+(xiy};2Z~I1.
(S.A4)
Nothing new is obtained since this expression says essentially the same thing
as formula (S.Al) or (S.A2). However new results can be obtained if we
raise this invariant to an integer power, I,
X, =:
e'"",,'+m<p~(x, y, :z)~
(5.A5)
L
In
In the righthalld side terms of like powers in , and 11 have been grouped.
Each coefficient is a function only of x, y and z. Both the monomials in , and
11 and the polynomials in x, Y. z transform. according to a certain representation. Hence knowing that
form a basis for an lrlYJducib/e represen"'
tation we conclude that the qli'(x,)', z) do the same. It turns out moreover
that the functions, constructed in this way are actually the solutions of the
Laplace "equation. This is not surprising since one of the properties of the
Laplace equation is that it does not change under a rotation of coordinate
axes. Its set of solutions, forms a representation of the rotation group and it
is possible to choose the solutions in such a way that they form an irreducible
represe~tation. Hence we conclude that the solutions of the Laplace equation
should: be a linear combination of the polynomials we have constructed
above. f
If we went into more detail we could show that the polynomials are
actuany, up to a mulplicative constant, the wellknown spherical harmonics~
(See KttAMBJlS [1937], page 170.)
,'_,,'+m
Appendix
OD
this fact.
174
[Cll.. 5
of
M+ 1 M_ 1 M_ t M+ 1 =
M_ 1 Nlz Mz M_ 1
M s M+ 1 lVl+ 1 M:r
2M~
(S.A7)
= Ml
= M+l
(5.AS)
(S.l\9)
M2 =
M;+M;+M;
= M+1M_l +MIM+l
2
== M+IM_IM.+M;.
+M;
(5.Al0)
Aswe have seen, Al2 represents the square of the total angular momentum.
This is an invariant 9f the rotation group, which consequently commutes
with aU the operators of this group; in particular with M", M, and Ms.1
We have now to find all the possible systems of three matrices M + l ' M  t
aJ1d Mo that satiSfy the preceding conditions and form an irreducible linear
group.
, Let ~ be an arbitrary representation of )3 and Dto the corresponding
'representation space~ Ito is a subspace of the function space 81, invariant
with respect to the rotation group~ We can choose in this subspace ~l
system of basis functions t/l1mt' finite or infinite, (we explain in a moment
why we use two indices) for which the abelian subgroup ~1. of rotations
around the zaxis is completely reduced. In other words the basis func~ions
.dre chosen in such a way that a rotation 8%, considered as a change of coor. .
dinate axes (compare Chapter 4, 2.3) induces the transformation
APPENDIX II
Ch.5]
= .[(2 I
Iml
IKf.
(S.AI1)
(S.A12)
"'m+1,'
where (m + 1) is constant and n takes all possible values. As the last are only
defined except for a unitary transformation, we can take M + 1/Imn itself as
basis vector under the condition that we multiply it with a convenient conHt~~"n.t to n.orma.1ize it. The same considerations hold for ~f 1 V1"". in the
176
(Ch.5
eigenspace (m 1) of the matrix M Hence, if we now suppress the index "
which became
.Interpretation:
~ ~
:a
0; M 11/1"
= Q.
(S.AI3)
M.t/I", == mJ/!m
the ". and p. are numerical factors. Thls, together with (S.A7) and
(S~A13)
gives:
1
l/IJ ==
PJ~l"'j
1
'
1
M+.tJiJ2 == (M_ 1M+f.+ 2M,,)y,Jl = [PJtt!J+2(tl)]Y,Jl
(l,j1
ai1
== PJ2t/!J1
Pm == P.OC,.+l' we
= Pm+ 2m
(S.A14)
{J",l
Pj == 0, PJl
=:
2j,
JU+ l)k(k+ I) == 0
(S.AlS)
an equation that has two solutions. One is impossible: k =J+ 1, the other
k ;:  J is allowed. Hence, the sequence of eipnvalues of M., which we
have extracted in this way with the help of the operatOR M + and M _ , can be
written as j, j 1 t
U 1),
Ch. S]
In
APPENDIX UI
the value m = O. The sequence contains 2j+ 1 terms and since this numlx!r
should be an integer, j is either an integer or a halfinteger.
The cort'e'sponding eigenfunctions .p1' "'Jl,. 'tfi j span a 2J+ 1dimensional subspace UlJ invariant lvith respect to the rotation group, since
to
the functions transform. among each other under the infinitesimal operators
M +1, Ml' and M% of the group. The space is irredu.cible since the operators
M+l and Ml iterated in a proper way, will transform each arbitrarily
chosen axis I/Im into any other arbitrarily chosen axis !/1m apart from a multi. .
~licative constant.
Hence the representation D J which we have extracted from D and which
is determined by the infinitesimal basis transformations M+ 1J Ml' Ms is
an irreducible representation of tJ} 3. The representation turns out to be
identical to the one that is constructed in 2 and which was designated by
the same symbol.
It is sufficient to put in (S.i\14)
Pta
==
(Xm+l
= JjU+l)m(m+l)
that is
am =
.JiU+ 1)~(nll).
W"e again have equation (5.26) and we are sure that the basis functions are
normalized in the same way_
There is no other irreducible representation ~3 since for each representation D one can, by the preceding method, extract at least one representa...
tion D.i and if D is irreducible, it should be identical with Dj
Appendix
DJ1 XDJl
(S~34a)
= DJ1~J2+DJl*XDJ2t
(5.34a)
We have the following problem: The vectors in two unitary spaces are
subject simultaneously to the aame transformation of the unimodular unitary
group.
e~
= ~1 + Pf/l
'1~ = P~l+a,*fJl
~2
= cx.~2 + P'12
'12 =
fJ*~2+Ct'12
rx,a.* +
tJp* ...
Djl X DJ2
1.
of this group in
178
ROTATIONS IN
3DIMENSIO~TAL
SPACE
[eb.5
the three spaces Dilt' DlJa and mil x Uiil . In these three spaces we take as
coordinat~~, respectively: the (2j 1 + 1) monomials
..
_
q (i2)
2,JIlI2 
",2
'0
Y (j;z + ml)!(ilm'l)!
Qml m l
q(}t) q(i2)
1,
rill
2,
nil 
'
We have to decompose tIle space 9t)1 X laJ1 in nvo subspaces invariant under
the transformations (5.4), suell that the first: Dl)S+Jl is irreducible. To obtain
this result we will make a change of coordinates which replaces the Q"'I"'l
by linear comhinations of these quantities. Let us calli1 +j2 = J. We have
to find 2J~} 1 independent linear combinations, which. transform 81nong
each other, without intervention of any other linear combination, under the
transfornlation (5.4). They form the basis for the representation DJ1 ';'j:"
If we take el = e1 =
'11 = tl2 = 11 the last system should reduce to the
functions
e;
qJp
Th.~s
is
~j,d.l:=~t Vle
eJ +P 1'/JP
(P = J, J  1., . ,  J).
::=:=,_.
~v (J + P) !(J'  P) !
J==.
=
y.,7,jt j:2.h,
'::7
"'>}
/.=:::::.:
"VI~J
,&,
should necessarily makf.; a part of the basis of th.e ne'lN irreducible subspace,
since this is the only one whicll reduces itself to
c. 2J
i;;;
'\/21
if
= '2
and
"1 = 11
.A.PPEt~D I.X
Ch.. 5J
179
III
with
'PM = (2it)!(2j2)~
(2J)!
,_._
We state that the polynomials qJJ) l(JJl .... CfJJ are the variables or basis
functions of the representation D j1 +i1 It is evident from (~.A16) that they
satisfy the condition A and are consequently llnearly iIlde~ndent. 1 Let us
now verify that these basis functions transform among
other under an
arbitrary transformation of the group %' 2
each
e~'
PJ~
ae
+ b111
= b*el+ a*"l
==
(S.A18)
We have actually
with
= aCl.b* {1;
B = bct+a* p.
(S.A19)
Hence
(ae~' + p,,~)2jl((Xe~ +p,,~)2J2
a,J+MpJM
L 7}'I
"
 _.
XM =
L:  ..:.......::..:'.:.=::::::::.':':'~
hl
;:.. ...
!p 'AI
.J(J +M)!{c/M)!
group~ng
180
(Ch.5
term
'2"2
II
(5.A20)
These functions are of the dearee wanted and transform under a substitution
(5.4) exactly like the quantities P1II1"''j since the first factor of the righthand
side is an invariant. We have indeed
'1"2 "i e;
= C1 '12"1 ~2'
In this way we have found the basis functions of D J1 +JJ and DJ,,.XDJ2i.
We still have to show that each linear combination of expressions
Q 2 can be expressed in an unambiguous way in a linear combination of
ipJl and Q':
(S.A21)
where t/I is a linear combination of P",.m2' that is a. homogeneous set of
polynomials of degree ('i1 1) in '1' '11 and (2j2 1) in ~2"2.
Tb.tr necessary number of arbitrary coefficients, are provided easily since
we have,
(2Jl + 1)(~2+ 1) == [2Ui +j2) + l]+2Jl 2}2*
He~ce it is sufficieJit to show that the different terms
of (S.A21) are independent, that is that 4> cannot be identically zero unless all coefficients in the
rishthand side are equal to zero. Let us first take ~1 ::II '2' til == 112; the
last term in (S.A2l) is zero fP == 0 gives aJ := == a_J == 0 as the CPA{ are
independent. The QJI being zero, let us make ~1 :;.: (~t '11 ;' '12; tP == 0
implies necessarily '" == 0; hence the decomposition is unambiguous.
The representation D}t.. XDJ2i can be reduced in the same way as
DJI XDJ2 We &raue as before; taking (S.A20) and (S.A21) into account
we see that it is suftlcient to look for the coefticients in the development of
(~l!lZ '11 C2XrX~t +"'1)2Jl1(<<~a+J"JJ,hl
(S.A22)
in order to find the linear combinations of Q.1JW2 which serve as basis oftb.e
representation Dji XDJ2
181
APPENDIX III
Ch . .5]
If we operate this way, step by step, we succeed in expressing the decomposition (5.34) of the representation Djl XDj2 in an explicit form:
(we suppose' ~that j1 < i2)
tl> = l/Ijt+iz+(elYJ2f11'2)t/!jl+Jrl +
8
.....
+('1112"lel).t/lll+J2J. ....
(5.A21a)
(5.A22a)
(e
AI
171 ~2Y = l'~O ( 1)" v !(J. ~ v)!
A.
1112 
e:""I e; 17;"
}2
1Hl+mz=M
= flJ :}2
}2(1)"
v
C~lml Qml m2
(At! = J, J 1,
. ., J),.
(5.A23)
1nltm2=M
it,
i2
and A.. The index v varies in principle from 0 to .A., but one has to put
all ttfrms that contain a negative factorial equal to zero.
The coefficient C. t m2 is called the ClebschGordan coefficient, the Wigner
coefficient, or the 3j symbol. To calculate its numerical value is a tedious
task; fortunately tables are available (see references in Chapter 6).
The formula (5.A23) solves completely tIle problem of the decomposition
of the product Djl XDJz " It takes the siInple form (S.A17) if A = 0 and it
similarly simplifies in the opposite case: A = 2j2) J = il j2 Ul > i2)
1 The binomial coefficient of
('"I.:':
,,'"1
(OC~l
+{J'YJ1)2 J  A contains
 "
..:....I
(2j k.;,)
(R1]
)k
P 1
in order to have the total power of';1 equa.l to j~tm we take k = j'Pm and restrict the
summation to positive or zero values of this quantity., Similarly for ~2' 'I'J,
182
[eh S
,"

"
We can now give the equations (5.A21) and (S.A21a) a definite form, dis.
playing clearly the decomposition Dit X D i1. in its irreducible eienlentS., This
is 'the socalled Qebsch. . Gordan series
IJ1 Jll
L.
" "J
') PJ CimJ m Qmlml =
=J=Jl+J214=J
t;.", aM
ml+ml:;aM
J
JMtl
~"
J
J
LJ /J aMCf'M"
(5.A21b)
...f .M
The vector ifJ is an arbitrary vector of the space 91il X 8fJ:, that is a linear
combination of Qrnl m2" The 01 depend on the fornl of this combina.tion~
The PJ are normalization factors and the C;'tm:t are the constants determined
by equation (S.A23). The tpi, are the orthogonal vectors that span the space
It}I X ,all' those which have the same index span a separate invariant
subspace which transforms according to the irreducible representation D j
Their mutual orthogonality rt~sults from the orthogonality of the different
irreducible representation of the saIne group 1 (.1#3 for the indices J, !?d2 for
the indices kJ). We can write
But the Qm lm l = qf.l1 qf.~ are also orthogonal, sin(~e the fa\~tors q~\ and
q!:,. are;. Hence one can, keeping M = ml }nml constant, consider (5 . A25)
with Q""ml. The transformaas a ~tarytransformationconnecting film!
tion Imatrix is B ==
C!t_a)' where J labels the rows and ml the columns.
W~'can revene this transformation by expressing Q"Hml as a linear cODlbina~~~9f . ~~. Since B is unitary and real the inverse matrix is equal to the
transposed matrix, hence we have
2
Y'J
(5.A26)
The preCeding calculations have t~.en made V\tith the help of a partkwular
choice of basis functions lJ'!.:,., q!,.~ and QJftJm% of the representations DJ1 , Dh
andDJl ~I!h. But the results obtained are all linear hence they de.pend only
on the representations and all stay true no matter ~'hich functions we use
as a basis. In particular, we could repiac;e certairl ~ by 11;" and c.e~rtain 11 by
11;bS ltatementis only true in case every rel'resentation oo...'UfS only onco, a C".ondftioil
grOUPt
183
APPENDIX III
Ch 5]
4
,*, which do transform in the same way (compare 2.2). We can give in
this way a simple geometrical or physical meaning to the basis functions.
They could be
.. for example the Laplace functions, or more generally the eigenfunctions of an atomic problem. The formulas (S.A17), (5.A21b), (S.A23),
(S.A24), (S.AlS) and (S.A26) always apply_ This statement forms the basis
of the proof in Sec. 9 about the selection rules and the calculation of the
intensities of the Zeeman effect. In the majority of the applications i2 == 1
and
'
DJXD t == DJ + 1 +DJ+DJ 
&
S.A.l
J+l
yu+m+2~U+"'+1)
V2U+m+l)(jm}
)1
'vU
m}<;,m+l)
y.(jm+2~(Jm+ ~
VU+m+"l)Um+!)
V2U+m)(im+l)
2m
Ivu+m)(i~m)
l/U+m)Ut m_"
1)
This formula forms the basis for the derivation of the WignerEckhart
theorem and will be used in Chapter 6, 3, equation (6.17)~
CHAPTFR.
L;, L:,
Dop
r: =
..t
D pp' TIl~
p'= .1
(6.1)
T;
Y;.
are
T;
184
Ch. 6, 1 J
185
= Jtj
,2
,
A = 0 : constant
A.=l:Jz
1 = 2 : 1;!J2
A. = 3 : SJ;3J 2 J z +lz ..
We see that for ). :::; 3 the polynomials are different from the spherical
harmonics. The spherical harmonics are homogeneous in x, y, z of degree A..
The operator polynomials containterms of the degree A. and lower. Actually,
the concept of "degree" does not have meaning in this case, since with the
insertion of a commutator J z = (J xl y  J yJx) the degree can be increased
in a rather arbitrary manner.
Instead of pursuing the Schmidt procedure for It =F 0 a second, heuristic,
but sometimes more effective way of constructing the p~lynomia1s will be
indicated. Take a spherical harmonic and replace a term like
/
2xy
i.e~7
by
(.1 x ly+J yJ x )
take all possible arrangements and divide by the number of arrangements. 1"'his process leads to lengthy expressions which can be shortened
186
[Ch. 6, I
(6.2)
Its formal integration leads to an expression for the results of a finite
rotation (J) on the wave function "'(0):
(6.3)
(6.4)
(6.5)
Comparing coefficients gives us the relation
;.
[It, Tp]
=
""..
(I == 1, 0, 1).
(6.6)
Fro~1he explicit expressions for (1)p.p" well known from the Zeeman effect
= T;l IiJ(p=F..iXlIt+l)
(6.7a)
[10' TJ = T;hp
(6.7b)
Ch. 6, 1, 2j
187
L S == LxSx+L,S,+LzS.
(6.8)
the matrix elements can be calculated by group theoretical methods, ex~pt
for propotHonality factors. In ~ther word,s the ratio between the matrix
elements of such an invariant operator can be determined.
This separation of matrix elements into angular or geometrical versUl
radial or physical parts, is found in many different forms and the Wigner. .
Eckardt theorem is actually an example of many similar applications of
the following idea:
Suppose an operator 0 transforms according to a given (irreducible)
representation of the rotation group, say l and we want to determine its
matrix elements with respect to two sets of basis functions. One set transforms
according
to the irreducible representation j 1, the other according to i2.
,
This ;idea is not quite new, siIlce in Chapter 5 we treated this problem for the
special case of 0 being a vect<>r (i.e. ~ = 1). Given these irreducible represen~Uons the matrix elements will of course transform according to the reprentations contained in the direct product of the three rC'presentations
I
(6.9)
Usually some of the r /8 will occur more than once. 1 The general idea is
that the unitary transformation which performs this reduction is given by
group theory (actually the theory of group representations) except for a
1 In finite IfOUPS a multiple occurring representation may already show up in the direct
product of two representations, in the rotation &rOUp they are sinsly occurring
(Oebsch.Oordan series). With the direct product of three irreducible representations or
the rotation group, there are always multiple occurring representations, except in trivial
cases like it = ,0. Compare 4 on Racah coetllcients.
188
reb. 6 2
(6.10)
such that, they transform like irreducible representations. That is, hi. is a
~Jc~~ ~ the represen,tation is onedi~ensional), o~ a certain number of
bt,a,./qrm (in case the representation has more than one dimension) a basis of
an"'irJ/educible representation. If we integrate now, we find that all integrals
ov~/b, are zero, except bi which corresponds to the dftit representation.
'l:
pmm'
a!!,.,(ml0I'Jm')
= 41tc5 1i Jb 1 r 2 dr
01i
B t
(6.11)
If we take the inverse of the matrix a~~m' (i labels the columns and the triple
index labels the rows) we have the matrix elements expressed as a product
{6.12}
of'the radial integral Bl and a factor which depends only on the reduction
procedure". Hence this factor is entirely determined by representation theoryl
We went through this argument in order to stress two points. The first
the, question how many constants Bl are involved. This is now easily a~ .
~wered. The proof above was given for fixed values Ofjl,j'J, and A. We have ~Q
repeat it for every other
of values 11 and j2. How many possibilities
is
pair
Ch. 6, 2, 3]
WIGNERECKARDT THEOREM
189
does one have for a given A? That answer is given by the triangular rule,
which is of course the same condition as demanding that (6.9) will contain
the unit representation. For instance, for A == 1 the vectors i1 and j2 may
differ by 1, or o. Hence tlfere are three different constants Bl for every
given value of il (or i2). These three, or in genera121l+ 1, constants depend
on the radial shape of the wave functions and on the radial dependence of
the operator.
Since it is possible that there is more than one wave function with the
same jvalue, another quantum number t% may be added in order to distinguish
between the different (radial) wave functions. Hence B depends onj1 ,j2' ill
and (X2.
The second point is the remark often overlooked in importance that for
given a1 and/ (X2 the unit representation occurs once (or not at all). The
possibility of multiple occurring representations has already been mentioned
in a footnote. This is not the case for the unit representation. It occurs only
once, since the direct product of two representations contains each irreducible representation only once.
r). xrJ1
Lr
(i = l+ j1 , .. , lAill)
(6.13)
and the only way one can form r lout of the direct product of r j1 X
by taking i = j2. 1
This is not true for finite groups.
r i is
190
[Ch. 6, 3
bx +a,b,+'Q7,b= ==
b  l +aobo+atb+l
(6.8')
where al == 2+(a.ia,). In the same way we can construct invariants out
of tensor components provid'ed
take irreducible tensors and label the
components in a proper way. The construction ofirreducible tensor operatob
a priori 'has been considered in the previous section. It is only necessary to
define them ~ere as quantities that have the same transformation propertlel
Q3 the spherical harmonics. The general form of an invariant coupling will be
Dx
Q+l
we
01=0
== H coup1 ==
p.c  l
T:(1)T~p(2),
(6.14)
where the first operator acts on one type of wave function, the other on another type of wave function. These were originally the spin and orbital wave
functions; we call them 1. and 2. They may have irreducible representations
Ch. 6. 3]
WIGNBR..BCKHARDT THEOREM
191
(6.15)
L
AD;./ JD;;n1 j'Dnl(mITyln).
wnn
(6.16)
SQ f we have done nothing but explicitly expressed the fact that the bases
and the tensor. components transform according to irreducible representations. We can now, using again the fact that all rotations are determined by
the 'ame set of Euler angles, apply the ClebschOordan reduction formula as
expresse4 in,Chapter 5, Appendix III, eq. (S.A27),that is we .can~~ethe
product ~AflJt by choosiq a linearcombillation. such thateach.Gf~these
transform according to the representations j" == J.+j, A+11 .. _IAjl:
(6.17)
and after this substit~tion we,let the parameters (Euler angl~) contained in
S run through all pOssible values. We integrate over theSe variables and
apply the orthogonality relations between the matri"t elements (see Chapter
3). As a result (6.16) reduces to:
192
.;
,
'"
[eb. 6, 3
A
= Ci',i
<5,,+m, n(jml7:IJ.'n).
bIl + i, I "L.J Cl',}A
pk
\pm
2 ., 1
"
'J
mnv
(6.18)
VIITIlj') =
2j' + 1
m, ..l'
VmIT"Ij'n).
(6.19)
The result is that the ratio between the matrix elements (jkIT"lj' /) for different k and 1 values is completely determined by group theory. The proportionality constant depends only onj,j' and whatever other quantum numbers
are used to describe the system. The double bar matrix element is called the
reduced matrix element. It is at this moment that we see the full importance
of the ClebschGordan coefficients in physics.
Introducing the notation 1 used by CONDON and SHOltTLBY [1935]:
(j1 m llr;Um ) =
l)Ait +j
(AJljml.tjit m l)VlIT).fj).
(6.19a)
2i1 +1
(rxjli2,JMI
T;(l) T~"law'j~j~JM>
I'=A
(6.20)
We will come back to eq. (6.20) later in 4. Eq. (6.19) has a wide range of
applicabilities; for instance transitional probabilities, that is, matrix elements
in which j' rI= j. One can, of course, also deduce transition probabilities from
(6.20) by taking as one of the tensors the field that causes the transition.
Besides the application of (6.19) to the calculation of the dipole moments"
1 Compare EDMONDS [1957]. This monograph contains a very practical table that
indiCates the connection with all other notations. Our Clebsch.. Gordan coeflicit"ftt is
related to Condon and ShortIey's by:
J
CmImi
==
(jlj"JMlil mJ.m,,).
Ch.6,3,4]
RACAH COEFFICIENTS
193
which will lead us again to the expressions (5.48) it is also easy to determine
the corresponding equations for the higher multipole moments.
Another application is made in crystalline field theory where the potential
energy is replaced by a linear combination of irreducible tensors that have
the same symmetry. The matrix elements of the energy and, after diagonalisation, the eigenvalues can also be determined with the WignerEckhardt
theorem. The result contains a number of undetermined proportionality
constants. This is not surprising since the replacement Hamiltonian fulfilled
the necessary condition of symmetry, but is not sufficient to describe the
physical situation adequately.
4. Racah Coe8icients
The Racah coefficients were originally introduced in polyelectronic atomic
spectroscopy in 1943 and subsequently found a widespread use in nuclear
spectroscopy_ They are also useful in solid state work. If the crystal symmetry
is introduced through an operatorHamiltonian, sooner or later in a physical
calculation the coefficients in front of the different terms of the operator
expression have to be calculated. It was realized that these coefficients were
similar to the reduced matrix elements and hence connected with the Racah
coefficients. In the following pages we will follow Rose's treatment.
The idea ~f a Racah coefficient is as follows: If two electrons are coupled
the qebschGordan formula states which irreducible representations are
contailned in the product representation, and that each of these representations is contained only once. However, if three electrons are coupled the
irredncible representation of a certain finaljvalue (total angular momentum)
may occur several times. This indeterminacy is shown by couplingjl withj2
into j' and coupling j' with i3 into j. As a result there is a set of mUltiple
occurring irreducible representations. However, if i2 and i3 were coupled
into, say, j" and subsequently j" and il were coupled, then the resulting
bases would have been different. Of course the product representation will
contain the same set of representations each with the same multiplicity.
Since any linear combination of equivalent irreducible representations is
again an irreducible representation of the same type, the two different
coupling schemes may give different results for the bases with respect to
these multiple occurring representations. The Racah coefficient gives the
relation between these:
(6.21)
194
[Ch. 6, 4
. 4
Plg. 6.1. The coupling of four ansuiar
momenta.
l'
tlic .
J",.
Ch. 6, 4]
RACAH COEFFICIENTS
195
was decomposed intojl' andjli is not uniquely determined, and an the different values of jl1 (to each of which belongs a certain i2') will give a contribution to matrix elements of the bilinear operator. Each of these contributions
has a coefficient which is completely determined by the rotatiow transformation properties. They all have the same proportionality constant: the
"strength" of the coupling. The result of the decoupling and recoupling is
equal to the product of this "strength" constant, denoted by (IIT"(I)II)
(11 TA(2) II ), and the Racah coefficient. Hence, if we take the contracted
(6.22)
and coupling the resultant with j3 gives:
'"Jm(j') = ",tL C~''''3 "'i'm' 1/1JJ m3
(6.23)
m3
(m' + '"3
=fII)
"'JII.(}') ==
(6.24)
"' .....z
In the same way "'J,.(j") can be found and (6.21) will take the following
form
(6.25)
Multiplying by JjJ )11'1 t/I J2Jj;J "")IIA' will give a set of ~ functions at the lefthand side which make ml =: JJl; m' m:t == Jl2 and mm' == 1'3. i.e. there
are only two summations over the ",'s since the third is determined by
P1 .+ fJ,,. + Pl == m ttnd similarly on the righthand side. The result is:
li c'
. . ,~ R ii" CJI'lJj3
" "..J
e"'~"lJA1;
Pl+Pl.l'l =: 4.J
\';,J1.tl'::+Ill "
1"
'II
orthogon:?~tity
Using the
196
[eb. 6, 4
subscripts) we find
(6.26)
~.
'"
= (1)il+i2+J3+iW(i1i2jj3;j'j").
Ch. 6, 4)
RACAH COEFFICIENTS
197
is
CHAPTER 7
SPACE GROUPS
1. Outline
In tJUs and the following ,chapter we 'will display those groups that are
used in !lonrelativistic physics in general and in quantum mechanics in
particular.
The most important group is the full rotation' group.;,The exte~sive treatme~t qf the r,~presentations' of this group was gi~eIl.in two of'thd previous
chapters~Th~~fulrrotation group is usedin the description ot.isolated,atoms
and ion~. Itaiso pJaYS a role in the ~asic description of tp.e wave function
in general, irregardless of the symmetry, since the representations of the
r"II rotation group serve as a starting point for almost every calculation in
quantUJll,. mechanics.
.
In dea.liJ1g with crystalline solids, however, another type of grouphasto
cOnsi1ered. ,The most strikin~ property of a crystal is the re~~rity of its
structjure.
. If this structure is perfect, i.e. no errors, infinite in siZ .and free of
temMrature agitation, this property can be expressed 'by saying that certain
tran~ations are allowed. It is to be expected that a number of physical propet1ies are invariant under the operations of this group and so it would be
interesting to study the group properties.
. Besides these translations, rotations of the crystal that will bring the lattice
into complete covering with itself are possible and the group of translations
may be extended to a larger group, the socalled space group, which contains
both. The meaning of this synthesis in group theoretical terms will be discussed in 4. First the space group will be considered as a totality and then
analyzed in rotational and translational parts .
The space groups contain elements which represent pure translations,
elements which represent rotations around a center a~d elements that represent both. The elements representing rotations will be shown to form a
subgroup. These subgroups are called the crystalline point groups.
The third set of groups of interest in quantum mechanics are the point
2
'
198
be
POINT GR.OUPS
Ch. 7, 1, 2]
199
groups, i.e. th.e groups representing a finite set of rotations around a center.
These are ~~ed in molecular problems. The crystalline point groups are a
special case of the general point groups . For instance, the five rotations over
~1t around a certain axis form a point called C s . Thisisnotacrystallinepoibt
group since it is impossible to construct a periodic structure that contains
a fivefold axis, since one cannot cover a plane completely with pentagGn<s.
Most molecules happen to belong to the same point groups that form th.e
crystalline point groups. There are exceptions and nature seems not even to
"abhor" fivefold symmetry~ Th.ere is a substance called Ferrocine that
contains a 5';'carbon ring.. The a(,'tual shape of the molecule is somewhat like
a sandwich of two of these rings with an iron atom in the middle such that
the symmetry around an axis perpel1dicular to the rings is tenfold.
The relations between the sets of groups are as follo\vs:
2~
~
3. Point groulls
Space group
~
4. Pure t.ranslation
l~
200
SPACE GROUPS
operations of the group (rotations, refiections). 'This point will remain the
same distance from 0: OP = OP'. If the group would be infinite all the
points P' wDMd cover a circle. From consideration of the ~pace group it will
be seen that any point 'in the lattice can be described by a set of integers.
Hence all operations can be described by a representation which uses only
integers. This is again true for the point group contained in the ~pace gro\1P.
Any representation of the crystallographic point group is equivalent to a
finite group of linear substitutions among integers. This important conclu. .
sion, which is fully described in the next section, leads in a very simple way
to the restrictions on the order of the group (compare BUltCKHARDT [1947]).
An arbitrary orthogonal rotation in two dimensions
X' = x cos cp  y sin tp
(7.1)
y' = x sin qJ  Y cos <p
can be conveniently expressed with the linear combi,nations x+iy and xiy,
which gives rise to a transformation matrix
iqJ
e
( 0
0)
e iql
(7,2)
Since
(7.3)
the ~ible values of n are n == 2, 1, 0, 1, 2. Let e f., == e then multiplyin, (7.2) with 8 gives,
2
(7.4)
8 ne+ 1 = 0,
8n"equation which can be solved for the five different values of n:
2 gives
n = 1 gives
n:=
n
n
=
=
8
8
= 1
== i(1i.J3)
0 gives 8 = i
1 gives e = t(1 i.J3)
2 gives e = 1.
(7.5)
Ch. 7,
21
POINT GROUPS
201
Fig. 7.1. A tetrahedron can be imbedded in a cube showing that its rotation group has to
be a subsroup of the cubical group.
!
202
SPACE GROUPS
[eh. 7, 2, 3
cular Fig. 7.1 servesto,illustrate that T is, a subgroup ,oro. Another method
is the stereogr~phic projection. Table 8.2 gives all the' crystallographic
point groups. The extension to noncrystallographic point groups is easy to
establish and can be found in the chemical literature. 1 A third method
using pieces of cardboard has been described by SCHIFF [1954].
3. Space Groups
After the intr9ductory remarks in 1 a notation must be ~sta.blished for
the elements of th.e space group. These elements consist of a combination of a
rotation and a translation. By rotati,on we mean a P1l!e rotation, a reflection.
an inversion or a combination of these . It should also be pointed out that an
element may be a product of a rotation without translation and a translation
without rotation, but that this is not necessarily so.
In certain space groups there are screw elements, that is operations consisting of a translation and a rotation which is not a product of a translation
without rotation and a rotation without translation where both are elements
of the groupthemselves . The screw elem.ents do occur in nature, for instance,
we know of the existence of optical effects, such as the rotation of the
polarization plane. This occurs if the index of refraction for left circular
polarized Jtjght is different from the index. for right polarized light.
The mo~t general translation allowed in a threedimensional crystalline
strtlcture is described ,vith help of three primitive translation vectors a, b, c.
These ale three non..coplanar or independent vectors~ that is
/
a(bxc)~O
(7.6)
chosen in such a way that they represent the smallest possible translations.
We will see later that there is a certain 'ambiguity in the choice of these
vectors altho1.1gh not quite as large as the choices of basic vectors in a
vect()r space.
The general translation is
(7.7)
where n l ' n2, n3 =s 0, 1, 2, . ., ..
The"pure translations are not the only possible operations allowed in a
t
E'i:~lNG! VVAVI'!.R
and
KIMBALL
Ch. 7, 3]
SPACE GROUPS
203
Xl
= R 11 X 1 +R12X2+R13X3+TtX1
= R 21 X l +R22X2+R23X3+T2X2
x~
x~ = R31Xt+R32X2+R33X3+T3X3
(7.8)
(7.8')
(This differs slightly from the convention used by SEITZ [1934] where the
rotation is written on the left, the translation on the right in order to preserve the usual order of operations: from right to left.)
A possible representation of A can be obtained as follows: The operation
A on any T should result in a general translation. In particular if we operate
on a primitive translation vector
Aa. =
n~a)a+n~a)b+n~ll)c
2)
the
= (Olb ij)
or
(OlE)
(7.9)
Fig. 7.2. Illustration or the product rule for space group elements.
SPACE GROUPS
204
[eh. 7, 3
(7.10)
The product rule can be illustrated with a simple diagram (FiS 7.2).
A certain" Point taken initially at 0 and a certain direction in the crystal
taken parallel to the xaxis undergo a rotation R1 and translation T 1
This is followed by a second operation (T2IR2)' The translation axes are
fi.xed in the crystal, hence the second rotation will rotate the vector 11 ,
or to say it differently, the second 'operation takes place as if the origin had
been at 0'. Hence the total translation is not T2 + Tl but T2 + R2 Tl .
3) The inverse element is
(TIR)l
= (R 1 TIR 1 ).
(7.11)
:=
(7.12)
Due to their Abelian character, a group element of this type can be unambiguously written as the product of three group elements, each represent.
ing a translation in a certain direction.
4) The associative law holds: This proof will complete the demonstration
that the combination of rotations and translations indeed form a group.
Let the operator (T3IR3) act on the product of two group elements,
(T2IR 2 )(T 1 IR1 ) = (Ta +:a.,l T1 IRz R. 1 )
= (T3+R3(Tl+R2Tl)IR3(RlRt).
(7.13)
= (TRR'R Tln'R.
(7.14)
using (7.11) and (7.13). This is clearly not an element of the point group
Ch. 7, 3]
SPACE GROUPS
205
(except in the trivial case that R' = E). This result is independent of the
presence or absence of screw axes.
The 1triplc product (7.14) can also be illustrated with Fig. 7. I. The second
operat~on will transform 0 into 0' and the third operation will translate P'
backwards to 0', instead of to 0 with the result that the triple product does
not represent a pure rotation.
On the other hand, if pure translations are considered it is immediately
seen that they form a subgroup (Abelian), but this subgroup is invariant,
(TfR)l(T'IE)(Tllt)
= (R 1T'IE)
(7.15)
using (7.10) and (7.11). The result follows immediately from (7.13) since the
total rotation is
R3R.2Rl
= alEa =
E,
206
SPACE GROUPS
rCh. 7, 3, 4
crystal, which has the same structure except that one type of site is filled
",~ith a Zn and the other with an S, the screw element is excluded.
A ted!()"tIs analysis shows that there are 230 different space groups. They
are a combination of one of the 23 point groups and one of the 14 different
translation patterns. A translation pattern is illustrated by a space lattice or
a Bravais lattice. These Bravais lattices are the space groups in which there is
one atom per primitive unit cell (i.e. the unit cell spanned by the three primitive unit vectors). In order to bring out the system (a system is characterized
by the number of 2, 3, 4 or 6fold axes) to which these Bravais lattices
belong, the socalled conventional unit cell is used. This cell has a volume
twice or three tinles the smallest unit cell (compare PHILLIPS [1956]). In
quantum mechanics it is convenient to introduce a more symnletrical unit
eell, the WignerSeitz cell mentioned in 6.
\
f/~2~. ~1.
The converse statement holds also. If (i) c 1 and ~.2 are invariant subgroups
of <#, (ii) the elements of t!J consist of the products of the elements of t[lt
and the ,elements of (12 and (ill) the elements of < 1 and l 2 have only the
unit element in common, then the group C is the direct product of ~ 1 and
!l. That is a given element of t can be written as a product:
Ch. 1, 4]
02
are determined by
207
[1937]
There.are less restricted ways to form products of groups: the weak direct
product and the senlidirect product. Both are generalizations of the direct
product mentioned above, but their nature is entirely different.
The weak direct product (MELVIN [1956]) has instead of commutability,
the requirement that the product of an element of c 1 with an element of f' 2
should give an element of < such that
/here G; is another element of t2 and G~ another element of 91 1 , requirements (i) and (iii) are maintained. The weak direct product is the most
general product, because it does not require any subgroup to be normal
(compare problem).
/\.. third type of direct product is the semidirect product (McINTOSH [1958a].)
Let fJl and ~ be two groups and suppose fR is an operator group for f.
That means that an element of (Ji operating on an element of rJ results in an
element that belongs again to ~. A group can be defined by stating that its
elements WIll consist of a combination of one element of fJl and one element
of ! such that the product is defined by the rule
(G'iR')(GIR) = (G' R'(G)IR' R)
(7.16)
wher~ R'(G)
SPAC~
208
GROUPS
(Ch. 7, 4, S
1.
Ch. 1, 5]
209
((Ja(r) = q>(rRIJ),
(7.17a)
If'(,  Rb)
. (7.17b)
lfJb( r)
:=
Fig. 1.3. Two center coordinate system used for diatomic molecules.
The two wave functions are the same functions if taken with respect to their
centers. The most general zeroth order (i.e. product type) wave function
~ch can be set up is
I
: t/J
(7.18)
/ In the ionic case both electrons are at one center, say b. Hence C1 <<:: C1
and, since exchange is disregarded, C3 == C4 == o.
In the covalent case take C 1 == C1 == 0 with C3 ==  C4 , the only possible
combination that is antisymmetric. The binding is the result of a spinzero
state and since the total wave function has to be antisymmetric, the orbital
part has to be anti.symmetric too. This type of wave function gives rise to
exchange integrals and as a result of that the charge density at 1(2" + R,,)
Yll11
increase.
reh. 7, 5, 6
SPACE GROUPS
210
and
or
C1
= C2
= C3 =
c4
To summarize this the following list for the two electron two center case is
given:
Ionic
eonvalent
Metallic
C1
Cs
Ca
C,
large
small
It is assumed that the Nelectron Ncenter case shows the same characteristics. This undoubtedly is true for the ionic case, to a lesser extent for the
covalent case. The metallic case needs considerable improvement and it is
here that the fullest use is made of the space group.
6. Pure Translations
Sr
=,.' =
Rr+T,
(7.20)
where
l'
PURE TRANSLATIONS
Ch.7,6]
211
ary condltions are involked, which' is not necessary but convenient, we find
x,
(7.24a)
,..
(7.24b)
(7.24c)
= eiltl/Nl
(7.2Sa)
p = ei"'21N
1 + ')' = elh3/N3
(7.2Sb)
= 0, 1, 2, . . . , N 3 1)_
(7.2Sc)
a,Nl
=. 1 .
pN2
= 1
yN3
+
ex
(h 3
an
1"
to
SPACE GR.OUPS
212
[Ch. 7, 6
(7.2Sc)
nlQ.I+nlb.+nsc. == z.
(7.29a)
"2 == Vl{(cxa)~x+(cx.),y+(cxa)%z}
(7.29b)
(7.29c)
v == II <b x c).
(7.30)
where
* ==
II
bxc
,. (bxc)
b*
==
eXIi
II
(bxc)
axb
; c* == .11,.
(bxc)
(7.31abc)
which have the following properties as is easily verified by equationi (7.31 abc)
11* == 1 4* b == 0 a* c == 0
b* == () b*" == 1 b*. e == 0
c ." ::: 0 c* b = 0 c* c == 1.
Hen~
(7.32)
(7.29)
The numbera hi, h2 and hs could be used as labels for the different irreducible representations. Usually it is preferable to use:
(7.30)
Obviously this vector " can attain only a limited number of values. This is
usually expressed in a geometrical way, i.e. by stating that Ie can only
1
The asterisk caDDot be confused with complex conjugate, since these vectors are real.
Ch. 7, 6]
P1JRE TRANSLATIONS
213
occupy the points of a certain unit cell in an abstract lattice. The lattice
is called the inverse lattice, and is generated by multiples of the vectors
a*, b* ana~c* in a space called the inverse space since the unitlength is the
inverse of the conventional units of length, like em 1 etc. The unit cell is
mapped out by the condition for hi' h2 and h3 mentioned in (7.25abc).
Technically speaking this unit cell is a half open point set, i.e. all points at
the boundary at one side are included, all points at the opposite boundary
plane are excluded. The reason that one should not take both ends is that
they differ by a distance a*, b*, or c* depending on the pair of planes one is
considering and hence are equivalent points.
Instead of the condition (7.25 a.bc) any unit cell ill the inverse lattice will do.
The most elegant choice is the unit cell vvhich was introduced by WignerSeitz in their ca1culations in the direct lattice. This cell is obtained by considering a lattice point and its neighbours and erecting planes half way,
between each atom and its neighbours, and perpendicular to the connecting
line. This unit cell is called the (first) Brillouin zone and would have been
established directly if \ve had used the following range of h values:
= 0, 1~ ... , !(Nl);
 0 ,...!..
l 1,
.J,""
..1. "', .. ..
(7.25')
Bloei.~
'lneorem
214
SPACE
OROU~PS
[eb. " 6
z.
I
7.4(3)
7.4(2)
7.4(5)
7.4(4)
,
I
~A
X
",CY'
,;
0  . 
7~4(6a)
'(
.v
7.4(6b)
Ch. 7, 6]
PURE TRANSLATIONS
215
7.4(7)
7.4(8)
7.4(9b)
z
,
f
A~
I
I
i
l
,
I
rf4
Ao
/ / ?'M
710)
r~_..g_
/~;
;x
'c'
216
[eb. 7, 6
SPACE GROUPS
z
7.4(11 b)
7.4(12)
z
z
7.4(13)
7.4(14)
Ch. 7, 7, 8]
217
(7.32)
where u(r) has the same translation symmetry as the lattice that is if
V(r) = V(r+ T)
+
(7.'33)
(7.34)
where u,,(r) is periodic with the periodicity of the lattice and. is in general
dependent on k. For a given value of k there may be more than oneperiodie
function u" hence one has to add another label to distinguish. these different
"branches".
218
SPACB OROUPS
[eb. 7, 8
(7.35)
is the expression of the abovementioned procedure. We also see clearly the
'JDe&nina of the reduced wave vector emerge, that is the wave vector inside
the Brillouin zone.
The periodic function
u(x+T} == u(x)
(7.36)
.,It
Pt.. 7. 5.' J!aav u a ftmctioD of the \lDJ'eCluced wave vector (or exteIlded Brillouin zone)
.for a tree pardcJ.e.
*"
Ch. 7, 8]
219
...
,. If
Pia. 1.6. BaeraY curves in tho UDreduced wavo vector space, for particles in a periocIic
potential.
t
220
SPACE GROUPS
Ch. 7, 8 9)
fourteen Bravais lattices there are also point groups in the reciprocal space.
These point groups mean that certain sets of k vectors may be the basis for
a group. elf. the same or of lower order. This idea was worked out by
B:ROUCKAER.T, WIGNER and SMOLUCHOWSKI [1936]. A short review of their
ideas will be given in the next section.
(7.37)
r,
where
represents the jth irreducible representation of~, S, the representation of .Tf' after omission of the elements of ~ that do not belong to ;F
and '14 the irre~ucible representations of :Jft'. The coefficients ca are either
zero or integers. This pattern is the major theme in many applications of
group theory in physics and the general case will be considered again in the
next chapter.
In $is chapter the special case where ,;'I' is a normal subgroup will be
consi*red. This case is, as we shall see below, of principal interest in the
appliq,tion of group theory to solid state problems. From the purely ma~
matiaU. point of view, the demand that .Tf' be normal is interesting for its
own/ sake since it leads to a number of important considerations.
Let usrecaIl that if the (abstract) elements B belong to I, than ABA 1
wjI1 also' belong to :Jft' (definition normal subgroup). Consider an element
A that does not belong to :Jft'. otherwise the statements would have been
trivial. \A different, way of characterizing the normal subll'oup is to say that
any "outside" elementwillindu.ce a permutation of the or4er of the e1~ments
in the subgroup .Tf'. The same statement will hold for the representatiou:
l
(7.38)
Ch. 7, 19]
221
S(ABA 1)
matrix
= r{A)r(B)r(A 1) ==
r(A)E(B)r(A 1),
(7.39)
and the
r(A) does not have to belong to the representation S.
If S is decomposed into irreducible representations with respect to ~,
a set of conjugated representations can again be constructed with help of the
different elements A available in ~ and "outside" ;t'. These conjugate
representations will again be irreducible (they are a permutation of an irreducible representation, hence if they were reducible, the original would
also have been), but not necessarily the same; i.e. nonequivalent;
= "",(B).
(7.40)
We would like to mention that 1", and 1" must have the same dimensionality and al$O, since all irreducible representations originating from r j are
each other's conjugate, we:find that all representations ,),,, coming from one
necessarily have to have the same dimension. All this stems from the fact
that "I,,' was connected with 1" by a permutation of the ulinks" between
abstract elements on one hand and the representation matrices on the other
hand.
If the element A is considered as a variable which runs through <D a set of
irreducible representations conjugate to y" is generated, this set is sometimes
called an orbit. Conjugation with certain elements A of t will produce
representations
which are equivalent to the original one. This will definitely
1
be true if A belongs to ,;t' since in that case the representation remains exactly
the ,; same. Also if this condition, i.e.
r,
1,,'(B)
= ,),,,(ABA  1) = 1,,(B)
(7.41 )
is fulfille4. for a certain element A, it is also fulfilled for all elements that are
in the same coset as A.
All the elements A that fulfil condition (7.41) form a group, the little
group ()f the second kind, .fRD. It is easy to show that these elements do
indeed form a group. For example the product rule: If A1 and A2 are any two
elemetlts, then
(7.41a)
y,,(A 1 BA;1) == 1,,(B)
r,,(A2BA;1) == y,,(B)
and the product element Ai A2 belongs to !!en because
(7.41b)
/'
",,(A1A2BAiiAii)
(7.41c)
222
SPACE GROUPS
:r.
r.
.r
(7.43)
T by:
(7.44)
(7.45)
rwt
Rk == 1c+2nK
(7.46)
Ch. 7, 9]
223
:Ie
0" l, 2 ...
mdicated m Fl,. 7.7 the points (r. M, X) and lines (Et A, Z) of sYriJmec:rYin
Icy
.+~M
the BriUouin~De. _' The little &rOUp belonsina to 4CO~~ of the u1li~
e1emontud diireftection with respe<:t to the klC~.l The
longing to r is tho same as the ,point group of tbelattJee':: D 4 Tlie'previOUI
two points wereex&mples of ,group elements that stay invariant,. urid8r tilt
condition (7.46) with K == O. The points M, Z, X su\.Y'not 'ofllyinVariant
unde~ certain rotations or refiections but also under a combination of these
with , translation. The irreducible representation of the special points or
lines ~ve been worked out for a number of Bravais lattices (see HEItMAN
(1958] and K()STBIl [1957]).
1iUJe,..,.pbe
The first type of question that can be answered with group theory in band
theory are of the same nature as the questions answered ":~ crystal fiCld
theory. Suppose there are r wave functions all be10qing to the same energy
level in the unperturbed state, what splitting of these , levelS win take place
after the interaction is taken into account? The level &~, i:.e., the number of separate levelS .u.d their depneracy, on tJlo.basis of,:these symmetry
considerations is called the uessential'" degeneracy. Whether separation
1
We mean
or course tho little poop or the Int kiDlL TIleUUle aroup of,.dle;'MCO~d
kind COD8iats of r tmd A', where It.. t, the reflectioB with l;apoct: to the x",ua.
that it, all pure traaslations plus all tranalatiODl combined with refteatiOlll arotmd the
xaxis.
[eh. 7, 9
SPACB GR.OUPS
really takes place remains to be seen from a detailed calculation, and if the
separation turns out to be zero, the additional degeperacyis called "acci.
dental" deaoneracy.
The names are rather unfortunate since there could be
.........
other reaSons, beyond the symmetry considerations, which made the
degeneraC1 not accidental at all. A famous example is the Fockargument
for the energy levels of hydrogen atoms. 1 The essential or symmetl)'induced degeneracies occurring in the special points mentioned above
~ be illustrated by two examples.
The energy of a plane wave depends only on the magnitude of the vector k ..
Hence all the four points: (0, k.~) == X, (0, k,) correspond to plane waves
that have the same energy. This holds in particular for the two waves
corresponding to X. The little group belonging to X, however, has only
onedimensional representations, hence the levels will split under a general
perturbation (the potential field of the cores). For symmetry reasons they
will have the same value at the points (0, ky ).
A second example is given by considering the four wave functions connected with M. They form a reducible representation of the little group
belonging to M. The last group is D4 and has four onedimensional and one
~~~:4~al~! representations. The representati9n resulting from the
four plane waves decomposes into two onedimensional representations and
one twodimensional representation (compare Table 7.1), hence under
TABLE
7.1
C.
C.
C.
C,
D4
.,wI
M,
M.
1
1
2
1
1
1
1
0
1
1
2
The 'wave equatioa of tile DOnrelativistic hydrogen atom can be written in a form
icloaticaJto the iatepal. equation for spherical harmonics in fourdimeDlioaal space. II).
Y8riaace UDder tile operatiODS of the last group leads to the ~Dclusion that the energy
1
levels with different L, but the same n, are desenerate. (Compare McINTOSH [1958b ].)
Ch. 7, 9]
22S
influence of the perturbation the fourfold level will split in two sinale levels
and one twofold level. This is often expressed by statina that two of the
four surftLCes "stick together" at the point M. This is based on the fact that
r is a continuous variable of the function k and a slight increase in Ie, say
Ie 4 k + Ak, will correspond to an arbitrary point in the BrillouinZone and
hence the four energy surfaces will, in general, be separated if one moves
away from M.
Compatibility relations and "accidental" degeneracy. The special points
in the BrillouinZone fall into two classes. Points like ~, Z, and A form a
locus given by the lines rM, MX, and rx. The little group of 4 should be a
subgroup of the little group of r as well as of X. Suppose we know the irreducible representation of the degenerate wave functions in X. If we move
away from X but stay along A the wave functions will span a reducible set
and the representation of the wave functions in X will decompose into a
number of irreducible representations of A. Conversely, this implies that a
given representation of A can go over into a limited number of representations of X or r. These socalled compatibility relations between the irreducible representations have been worked out by BOUCHAERT, SMOLUCHOWSICI
and WroNER [19361 and for the twodimensional (pedagogical) example we
give Table 7.2 taken from HEINE [1960].
TABLE
7.2.
Compatibility relations
Representation
Compatible with
r1rar.; XIX,
r.r,r:;; x.x,
r 1 r.r,; M1M.M.
r2rar,,;
Xl Xa;
XIX.;
M,Ma M ,
Ml Ma Ms
MsMfoM.
r.
226
(Ch. 7, 9
SPACB GR.OUPS
T,uLB 7.3
Character tablea
r.M
rM
riM.
l
raM.
r.,M,
riM,
.~
2. 4., 4:
1
I
I
1
1
1
mll
m.
1
1
1
1
1
1
1
2
1
ot r, M, X,
m.
m.,
1
1
1
1
0
J1, Z
.r1.EZI
~l.&lZl
~.z.ZI
1
1
2.
m.
Xl
X.
X.
X,
I
1
1
1
1
1
1
I
~,
1
1
1
m m m.
1
1
mil
1
1
1
1
of
SLATER [1934]
Ch. 7, 9]
227
and the dlike splits into a three and a twofold degenerate level. (Compare,
for example, Chapter 8, 2.2.) Using now the compatibility relations we can
state t~t ~from the slike level originates a JJ 1 representation (along the 111
axis), from the plike level ad; and a ~ 5 representation; (This last is twofold
degenerate.), from the dlike level a threefold representation giving rise to a
~5 and .4~ and a twofold level giving ~1 and .d 2 If curves are drawn between the end points, making sure that every curve has always the' same
representation, we see that ~2 and.4 1 must cross each other. Considerations
tt
If24, +.da
Ii; .d~+.d,
+:k...k
o~
.Pig. 7.8. BnerlY versus k curve of sodium in the Illdirection accordinl to HBiwNO (1937].
or
~ar
solid.
The implication of time reversal on the energy band structure has been
discussed by HmuuNG [1937a].
CHAPTER 8
FINITE GROUPS
1. Rotational Crystal Symmetry
Ch.
8.IIJ
229
TABU 8.1
Twodimensional point lfOapI
08
O ea'
@#.'
O
. @,,
O
''
,
0
C,
1m
Ca
2mm
elY
C 2v
C3
e 3y
3m
"
C...
4mm
C.. v
6mm
230
[eb. 8, 1, 2
FINITE GROUPS
8.2
Threedimensional point groups
TABLE
Triclinlc
o
1
Tetragonal
C1
J
C,.
Mon"ocllntc (2nd setting)
Q)
EBEB
EBffi
EBEB
\/f0
83 1....
Orthorhombic
f
\
C.
4'
s ..
4/m
C4h
I(T)\
. "'.....
422
mm2
ffi@,
.
B
.. 42m
..
21m
mmm
02hJ
'D2d
'
""i'A
. !~\
.. \./JV
'~
Ch. 8, t 1
231
( Contil7up.d)
232
FINITE GROUPS
feb. 8, I, 2
8.2
The thirty..two crystal point groups
TABU

International Symbol
Short
]
Schoen1iies Symbol
FujI
1
1
2
C.(C1A)
21m
nJ
222
mm2
mm2
i
4/m
422
4mm
42m
4/mmm
3
222
mmm
4
DIA(VM )
c,
i
4m
CIA
422
D.
4mm
S,
c,.
i2m
D ..(V.)
422
Du.
mmm
3
32
32
3m
3m
8m
!J~
6/m
C,(S.)
c.
222
mmm
C1
c.
c.,(S.)
D.
c..
Du
C,
c.
Cell
622
622
D.
6mm
6mm
8m2
8m2
C.1.'
D81t,
622
mmm
23
Du
6/mmm
23
m3
432
!S
m
43m
432
43m
m3m
~~
mm
paper is asymmetry plane, the circle is drawn with a heavy line. The stereograms are very useful except in the cubic case wh~re it is much. easier to
picture a cube instead of this rather artificial device.
Ch. 8, I 2]
233
In case of a purely ionic crystal, that is to say the case where the electrons arv ~ completely localized and belong to a certain ion or complex, the
wave iunction of these electrons or complexes will differ from the free ion
wave functions in such a way that the environment, in particular the nearest
neighbors, will produce a perturbation on the wave function. This result
may be hard to calculate particularly if the perturbation is strong, but it is
always necessary that the final wave function should have the proposed
symmetry. If the symmetry of the crystal is really known the number
of unknown parameters in the perturbation calculation may be greatly
reduced. Hence if the symmetry symbol of a certain point in the crystal
is known from the literature, it may be possible with the help of the theory
or representations to set up the symmetry adapted eigenfunctions. This
will be demonstrated in the next section.
Cons.ider a free atom or an ion, which has the symmetry of the full rotation
group, and place it inside the lattice of a solid. The allowed symmetry is now
restricted to the point group of that particular place in the solid. The physical
influence of the environment will be due to 1) electrical fields, 2) magnetic
fiet,ds, and 3) exchange interaction or covalent binding_
In general it is very difficult to give a complete calculation of these inftu~nces.
In certain cases, the socalled diluted paramagnetic salts, it can be
l
asSumed that the first influence, the electric field, is the most dominant of
the three. In this case a reasonable description can be made by assuming
electrostatic fields and ca1culating the influence of this perturbation on the
wave functions of the particular atom or ion. Fortunately, however, it is
possible to make a number of statements which are based on symmetry
considerations only and are completely independent of the actual physical
mechanism of interaction.
These qualitative considerations can be given with the help of grO\lp theory
or more correctly with the theory of representations. They were given the
first tinleby Bethe and simultaneously by Kramers.
Assume that a certain level in the free atom or ion was characterized by a
certain value of L or J and assume, in order to take a specific example in
mind, that the symmetry of the crystal is cubical, The Hamiltonian operator
H ul) will no longer be invariant under all possible rotations. The symmetry
j
234
FINITE GROUPS
reb. 8, 2
of the crystal ha~ reduced the number of rotations (which was 00 2) to only
those 24 rotational transformations which bring the cube over into itself.
Again lipply the theorem of Wigner, tb.at is, if cjJ belongs to E then also
Sy, belongs to E, except that S now refers to a restricted set of rotations. ~ro
formulate it more precisely, the group of transformations S forms a sub..
group of the original group, the full rotation group. Again we state that
dimension of the reducible representation is equal to the degree of degeneracy
of the level, since the number of dimensions of the boxes of the reduced
representation is nothing but the number of linearly independent wave
functions which belong to that particular eigenvalue. However, the representation cJlaracterized by L or J is now in general reducible with respect to the
cubical group. lhat is to say, if there are no common unitary transformations
which are able to bring the infinite set of matrices of the full rotation group
simultaneously into a form with s~aller boxes, there may be transfonnations
which are able to do tIns for the 24 rotations which correspond to the spacial
rotations which bring the cube over into itself. At first we are only interested
in the nurnber and k:.ind of irreducibJe representations of the finite group
which are contained in the origina12L+ Idimensional irreducible representation which is reducible with respect to the cubical group.
This program can be solved with the help of the characters of the matrices~
One of the important conclusions from th.is ll1ethod is that only the symmetry
detet;mines the pattern of the splitting of the levels . TIns, however, will hold
only!as long as the splitting of the level is small compared to the distance to
the rlext higher (or next lower) multiplet. In such a case the wave functions
of stlch a neighboring multiplet will have to be considered before starting
t~ considerations formulated above .
Before considering the general theory we would like to describe an example. In how many levels will an Fstate (L = 3) split jf placed in a cubical
field and ho"" large is the residual degeneracy? To answer such a question
the characters ofthe 5 classes of the cubical group in the (2[. . ,+ ))..dimensional
representation of the full rotation group have to be calculated . These are
easily calculated with the help of the following formula:
Note that the formula is derived for a rotation. around the zaxis (compare
(5.28) but the result holds for a rotation w around an. arbitrary axis, since
We have to choose for tb.e unitary matrix S (or U) a transformation that lets
the rotation axis coincide with the zaxis"
The five~lasses of the group of cubic symmetry corr'~'spond to the following
operations.
E Unit operation.
C 2 Rotation over 1t around each of the three edges (3 elements).
C 3 Rotation over !1t around each of the three edges (6 elements).
C 4 Rotation over 1'(, around the face diagonals (6 elements) .
C s Rotations over 11t around the body diagonals (8 elements).
Since each class always refers to one and the same angle of rotation,
that particular m in (8 . 1) has to be substituted. The result is~ for general
values of L, as follows 1 :
X E = 2L + 1 ;
"'c3=(1)[t
Tn this
s~cific
XE
X C2
L
];
Xc,=
X C4
{
= ( l)L
1 (L == 3n)
0 (L=3n+l)
,;;.,}.
1 (L '~ ~n+""\
(8.2)
'.,,;
== 7; X 2
= X ...
1;
X3 = 1; 's
= 1.
(8_3)
Now if trus set of characters is compared with the 5 irreducible representatiolls of the cubical group, then a linear combination of these five must be
fo+d such that each class has the values as given by equation (8.3): This is
doq.e simply by solving the five equations in five unknowns. The result is
gi)kn in the following table:
X
C.
e,
c,
Cs
rs
1
3
3
7
1
1
1
1
1
1
1
1
1
1
1
1
0
0
1
T,
If.
L=3
(8.4)
Hence the conclusion is that the F' level decomposes in two levels which are
threefold degenerate and one level '''hich is not degenerate. From this
simple >~ example, which can be worked out in a much more sophisticated
way<with the help of projection operators, we see that knowledge of the symrnetry is sufficient to determine the number of separate levels as well as
their degeneracy.
1 [iLl means the largest integer contained in !L.
236
[eb. 8,12
FINITE GROUPS
1
1
1
o
o
1
1
r.XD1
1
(8.5)
r r r r
I
L
:2
L
L.
f\lO nELD
NO l.'S
cue
NOLS
::
L
t1
L..
~
L'S
NOFiElD f
NO F"IELD
NO :5
variOllS
,i
f
_.1
conditions.
Ch. 8, 2}
237
r r
of L.
The L == 2 level has a basis which can be described by X2, y2, Z2, yz, XZ, \ xy
exclu4ing X 2 +y2+z2. The three last products transform like x, y, and z,
except! for inversion. Hence they correspond to one of the two threedimensionalrepresentations. The possibilities with the squares are restricted since
only two are independent x 2 + y2 does not work, since it goes over into +.:2,
using the rotation around the body diagonal which makes x . y, y + zand
z + x.. If this transformation is applied again, the result is Z2 + Xl. These
three functions together form the combination 2(x2 +y + r) which had to
be excluded. If the combination x2  y2 is tried, it leads to y2  rand Z2  x 2 ..
The third is a linear combination of the first two: z2x2 .. _().2_z2)_
(x 2  y2). After checking all the other matrix elements it is found that the
first two indeed form a (nonorthogonal) set of basis functions.
Slightly less haphazard is the use of spherical harmonics 1 (compare
j
Table 8.3):
In the following calculation the proportionality constant is of no importance. In
1:tpecific applications it should be DOuced that different conventions are used for the sign or
phase' factor of the spherical harmonics. These differences are lilted by EDMONDS [19571
1
on p. 21 ..
238
Flt~ITE
o  3z 2 ....... ,2
Y2""'"
Y21
GROt.!PS
feb.
_ ~...
~_2
x 2 """"Yu 2
......
(x+iy)z
Y22
8~
(8.6)
= (X+iy)2 .
Yi 
Y;
yi
o o o 0\
1 o o
E = f 0 o 1 o
\\ no 1
\0 o o o
/~
~)
o
o
~/
I  i
I
I
\ i
001
o
o
o
000
000
o 2 0
o 01
2 0
Cs =
0 0
0 0
0 0
2 0
0
1
o
o
o o
o o
1
0
\~
o
o
I
o o
o 2 o
o o o
o o o
1 o o
1
0 0
0 0
4 0
0 0
0 0
~\
~ ).
(8.7)
2/
= n" L X (i)C.
hiP.
,~
which is actuallyeq. (3.32) except that the character is real, we lind for
J.L == 3,5 (all others give zero matrices)
p (3)1I2) /+'
?JIV'
__
....l..
'~
(0IZ(3)!0) ~~ 1;
,+'>  .1 ..
/.,..~t~(3)f
,TkCt
,_
2'
< l[e(5)1 + 1) = t;
(216{S'f2) = <+2(8(5)1+2)
(8.9)
=i,
In this case the state vectors are already orthogonal. We find after normali
Ch.
8~
2]
i1\
! I'
(:2)
, 1'\)'/ I~;'i
.. !
 f  , t . J '\,J ,.{;".
r\ i
1>~
The symbols} 1m), refer to the spherical harmoni~s; for practical purposes
a table for I > 4 is included (Table 8.3).
TABLE
8.3
Spherical harmonics
= ar 2 (x 4 + y4 + Z4  3r2 )
(8.11)
240
FINITE GROUPS
(Ch. 8, .2
(8.12)
This satisfies Laplace's equation~ since it is assumed, that the charges that
generate the field are outside the atom. The constants, ~ are the parameters
which one hopes to determine experimentally.
The calculation of the matrix elements with respect to a set of angular
wave functions of given Lvalue is found by integration over three spherical
harmonics.
(L, M'IYl'IL, M) == (4n)t
f yf'ytyfd(J).
(8.13)
unit
Iplter.
The integral is only tIJI: 0 if; (i) M' = M +P and (il) the triangular rule is
fulfilled: A. ~ 2L. This means that the power series (8.12) actually is of no
importance beyond a certain term. The coefficients (8.13) are similar to
(5.42) (where 1 == 1) and in general to (S.A24) the Wigner or OebschGordan c~fficient. They are tabulated in the literature, l but for low Land p.
they can be computed quickly by employing the following integral
(ax+by+cz)211
=(4n)1 I (ax+by+cz)
2I1
dm
oil
'pltor.
(8.14)
3
0
0 7
0
0
0
0
JfS 0
0
S
0
0
0
1
0
0
0
Jf5
0 J15
0
0
0
5
0
0
0
6
0
0
0
0
1
0
0 7
0
0
0
Jf5
0
0
0
3
= (MIHcubI M ').
(8.15)
If rows~ and columns are interchanged this matrix can be reduced to one
onedimensional and three twodimensional matrices. The roots are A = 6
(3 times); ;. = 2 (3 times) and A. = 12 (once) in accordance with the
1
boo~ .
Ch. 8, 2, 3]
DOUBLB GROUPS
241
3. DoDIJle Groups
In Chapter 5 it was shown that representations of the full rotation group
could be obtained with even dimensional (irreducible) bases, corresponding
to halfinteger values ofj. This leads easily to the problem of manufacturing
a similar set of representations for a finite groupo The irreducible representations of the full rotation group are usually reducible with respect to a
finite group and with the techniques of the projection operations the problem
is solved in principle.
Before such methods are applied it is necessary to have the character
tables of the double groups. In case of the full rotation group it was seen
that the characters of the double group are different from representations
\Vith the help of spherical harmonics (if they were the same the representations would be equivalent!).
The s.ame is expected to happen for the finite groups. At first inspection
it looks strange that additional representations must be added to the
character table, since a wellknown theorem states that the number of
representations is equal to the number of classes and the latter is given by
the !abstract group table. It follows from this that we are actually not dealing
with the same abstract group.
The reason is that the representations derived from the spinon are not in a
onetaone correspondence with the different rotations of the finite group.
A' careful distinction must be made between a socalled nonfaithful
representation and the case we are discussing here. In the ,nonfaithful
representations a onetomany correspondence is dealt with in the sense
that to one representation matrix there correspond several elements of the
abstract group. Here the case is just the opposite. We have two representation matrices) one with the plus and one with the minus sign, which correspond to one abstract group element.
As a result the double group ?I' actually consists of 2g elements and the
number of classes is larger than the number of classes in the original group.
SinG'~ the abstract group is different, of course there can be a larger number
The fa(,~orisation of the secular equation has nothing to do with reducibility. The last
ternl only refers to a set of matrices. ,"n individual (normal) matrix can always be com. .
p]etely diagonalized.
1
242
Flt~ITE
GROUPS
[eh. 8, 3
factor group.
We will now show that the oppositeis not true. With the opposite \ve mean
that < is not an invariant subgroup of the abstract double group. l1his is
easy to show since t is not even a subgroup.. The two spinor variables ,
and '1 will transform under a rotation 17: around the xaxis according to:
(8.16)
(compare (S.7b) with lp = 1n; '" = in and :1 =m~ = x).
lienee if the elements of t;g are all the elements of C' witll only one of the
two signs, ~ inverse element of A cannot be included, wbjch shows that !JJ
IS not a isubgroup. This simple<illustration helps to stress the fact that tIle
double group is not simply a direct product of the single group and the group
consisting of the two elements 1 and 1 as is for instance the case if inversjon
.symm4try is added. toa group. Hence the structure of the do.uble group is an
intere~ing subject of study. The structure of the group 2t: can be described
as fOnpws. The elements Band R. form a norm~ ~ubgroup.Al'" of order 2;
the f,ictor group 2f/% is isoJ)lorphic to the ordinary point group. This
str~ture is similar to the structure of the space group [/'. There too a
notmal Sllbgroup exists, the group of translations !T, and the factor group
!Y/.r is isomorphic to the group of the rotations, The group of rotations
is not a su,pgroup of f/, similar to the fact mentioned above that the elements
of t' do not form 'asubgroup Qf2(. Both cases are examples of semidirect
products (Chapter 7, 4) of a group and an (operator) group. In both cases
we start out with the point group. The operator groups are either the
translations with the resulting semidirect product of the space group, or the
group cog$isting of E and R with the resulting semidirect product of the
do~ble group.
In order to establish the character table of the double group from the
original group fI, we first notice that if.the classes C i and Rei are different
their characters should be the same in those representations that qj' has in
I
Ch. 8, 3J
DOUBLE GROUPS
8.4
TABLE
Ot:
P for
and
243
double group
.
Cubical
No.
1
n'
xyz
2, 2'
3, 3'
4, ~'
~i
Ttyi
'Pz
1
1
5
6
7
8
9
10
11, 11'
12, 12'
13, 13'
14, 14'
15, 15'
16, 16'
17
18
19
20
21
22
23
xly
zy~
i
24
...
fJ
n'
V'
Element
~xz
xz5'
iyx!
t
t
t
0
.+"
.....
.B(R'== E)
C.
t/v 2
1/v'2
1/V'2
1/"\12
Cs
t
i
iJ
_.*
1
1
i/vl2
1/v 2
i/vl2
t
t
t
t
0
i{l +i)
!(1i)
i(14i)
!(1;)
i(l;)
i(l+i)
l(li)
t(l +i)
i!V2
(1'+i)/,l2
i~;f
1
'9%1
xzy
j;'
0
zYx
i
i
*!
it
i
fliy
yzx
0
0
z.iy
0
0
0
0
j
!
i:xy
Class
~iy
zxy
{J
:1f.
yxz
yx1
0
1
1
0
cp
<
j1ix
0
1
yig
YZ$
j
i
t
1
(1+i)/v'2
1/'\1'2
1/v'2
(1i)!v2
li,/2
0
~ilv2
1/v'2
=t=i/V2
i/v'2
=F (11)/v'2
1
1
!
t
*!
(Ca' = C~)
i/v'2
C.
1(1 +i)
!(li)
'i(l +/)
1(1i)
C,
!(lt;)
(C,,'':'' Cal
t(l~i)
i(l +0
1(Ii)
Hexagonal
Set 1: fJ = 0,
Ct = exp (bln/6)
Class
Element
Set 2: = 0,
fJ = exp,(inn/6j'
Class
" .....
Element
R
C~
('a
Col
4'
0
6
3, 9
2
10
8
4
11
7
5
1
I'
2,2'
3
4
3'
5'
6'
Cs
(''''6
~~
.~
71 7'
8, 8'
9, .9'
JO, 10'
11,11'
12, 12'
#'
J, "
1, 7
5~11
0,6
2,8
4,10
,.
244
PINrrE GROUPS
common with fI and should be the opposite sign for the additional representations.
Tho intcnstiq question when the classes will double and when they will
Dot has been studied by BBtHB [1929] and 0PBaI0wsIa [1940]. Opecbowski's
major result is: if there is a rotation around an angle 2E thel) the elements
c. and llCs beton, to the same class if, and only if, there is also ano~er
rotation throuah n around an axis perpendicular to the axis of the first
rotation in the sroup.
On the basis of this result he shows that the knowledge of the character
table of the 'liDsle" &roup is sufBcient to construct the character table of the
double lfouP. Almost all character tables can be found in the literature
(BBnm (1929): hexagonal and cubic; OPEcs:OWSla [1940]: rhomboedric and
tetrahedral; ELuan [1954]: for the space groups; JABN [1938]: for the
~ groups).
In Table 8.4 the necessary maredients to construct expUcit representations
of the cubic and hexasonal groups (and their subgroups) have been indicated.
The twodimensional representation is obtained by writing the matrix
a.*
( ,.,
II
P*)
ex
or
(txP* P)

Rep~tatioDl
Cb. 8. 4 J
OPERATOR HAMILTONIANS
245
ElI.pert.
==
1U
12 IH...1
E,,+AO
... +A E E
"
(8.17)
III
where H." represents the matrix elements of the perturbation operator with
respect to the UDperturbed eigenfunctions and Ell the unperturbed eipn
values.
We will show below that a similar formula can be given for a set of levels,
each of which have the same desenoracy r. The difference is that the symbols
H.. are now r by , matrices instead of numbers. The energy Ea...... is hence
expressed as a polynomial of matrices: the operator Hamiltonian. In I 4.3
we will see that, unless we are interested in numerical values of the constants,
perturbation theory is not necessary and the operator Hamiltonian can be
constructed on the basis of transformation properties only_
The situation, particularly in transitionelement ions, is such that each
level is characterized by an orbital quantum number L, a representation
label r, and by a label that numbers the different components (irreducible
basis ~~tions) of that representation. Since the 2L+ 1 wave functions
belo., to L usually decompose into several
which will in
be
1
relatively far apart (about 10000 em. ), the set of levels E" each be1onaiDI,toa certain
can be considered the unperturbed set in the same way as
above. 'ifhe eigenvalues E", E"" etc. were supposed to be far apart.
If th~ total spin function is introduced, we will find that the degeneracy
,factor qr every level is multiplied by 2S+ 1. The perturbation created by the
maanc~c
field will not be any different from a free iont i.e. 2S + 1 equidistant
!
leve1fJ.; unlessJhe spmorbit coupling is introduced. This interaction will
result in the symmetry restriction being "carried over" into spin space.
It was already demonstrated how a certain orbital symmetry
aadthe
representation of the full rotation group in spin space ~. can form a direct
product space in 2.1.
The spinoIbit interaction has no effect in the first order since
spin and
all orbit matrices have trace zero. We shall see in the next section that.tho
second order perturbation can be calculated in a way that bypasses the first
order and gives a closed expression for the energy splitting and the gfactor.
r,
aenn
r"
r,
an
PB~TURBAnON
THEORY
We want to formulate the perturbation theory with reference to tho tranJition element ions where the crystal field effect can be assumed to be larger
246
F!NITE (JR()tJPS
[eh. s. 4
this way:
>+ ;:
L#4
(8~18)
where the label i refers to the different energy eigenvalues in the electric
crystal field and the label k j = 1, ... , nj referfi to the cOlnponents of that
partiCUlar energy level. The degeneracy of tb.e level i is equal to nl" The
stubscript g refers to the ground state. rorhe ground states are known from
$und's:riiles. It could happen that the large electric field terms give rise to a
~gle ground state, in this case tIle orbital angular mome,ntnm is COl1sidered
ito be quenched, since the thermal energy is usually much smaller than; the
distan~~to:'~the nex.t higher level or group of levels. The result is that only
the lower level i is OC(:11pied and since the expectation value for the angular'
1110mentum of a single level is zero, the orbital motion does not manifest
itself anymore, or is "fr,')zen jn.H~ The other pos'itbility, namely that the
lowest electric field level is not single, occurs less often . It can be described
by a~~pseUdo angular mornentunl (ABRAGAM and PRYCE [1951]).
We wilt restrict ourselves fronl TI0,\V on to the first case of anondegenerate
ground state.
Ire'h~ry electron ,vave functIon is rnultipUed by 2 S' ~F 1 spin "rave fllnctions,
the degeneracy of allleveis is mulb,plied by a factor 281 1. It seenlS at fast
sight that this prohlen.l is rt~jated to the degenerate perturbation problem
m,entioned in Chapter 2~ '102 and 7.3. 11JC point is~ however, that this
problern it; slightly mort": com'P!iccJe(~ 8in':~G' the :spin. . lJrbit couplJng has the
Ch. 8, 4]
OPERATOR HAMILTONIANS
247
property that it does not lift the degeneracy in first order perturbation.
~ence ~ formalism has to be used that handles the removal of the degeneracy
~n the ~ond order. This'is conveniently done with help of th~ socalled
InteractIon representation. Transformation matrices are introduced such'
that the spin orbit coupling is transformed away in first order and a result is
obtained which expresses the Hamiltonian directly in the second order
contribution of the spinorbit coupling. In the next section it will be seen
that the result thus obtained is actually nothing but a special case of the
tensor coupling between the orbital angular B1Qmentum operator and the
spin angular momentum operator such that the internal product is an invariant. The method, originally invented by Van Vleck (see SCHIFF [1949])
is as follows:
Let the eigenvalue to be solved be expressed as:
(8.19)
if the matrix element of these operators is taken (the electrical field
contribution is already diagonalized):
Of,
>
(8.20)
In }the above development use has already been made of the fact that the
spinorbit coupUngis assumed
be small compared to the large electric
o.'ld terms, an assumption which is reasonably well fu1fiJ1ed in the case of.
iransition'elements. It is not necessary to make a similar restlictionforthe
small electric field terms since only the ground level has been taken into
ronSlderation and this was assumed to be sinafu so that the 'only contribittiOB
of the')'smaU terms will be a slight shift. Now choose the transformation
operator S in such a waythat it removes the first order terms
to
HS() + [Hcl' S] =
o.
(8.22)
(8.23)
Equation (8.22) can be solved very simply because the matrix eletnents of
1he electrical part are diagonal. Hence we have:
248
FINITB GROUPS
[Ch.8.1.
(8.24)
where E, and EJ are the diagonal elements of HelMU... If this result is
inserted ii! the transformed matrices H' the foHowing result isfounii for
the lowest level g:
= E~O)i<gl[H..,t S]lg)
(9IH',,)
= F,0)' ,.,
L (uIH.oII>(iIHlOlg)/(EjB.).
(8.25)
(8.26)
the final result for the socalled spinHamiltonian is found to be
with
Aid ==
L4 (gILtll><iIL,lg)/{E,E,).
(8.27)
if
~,
:lie1d~} ~use
<
Ch. 8, 4]
249
OPERATOR HAMILTONIANS
H.o+H.nr = CL S+J.(L+90 S) H
= <,S+pH) L+go/lS H.
(8.28)
resUlt is
H..+Hmf == gopS H ==
r'J A,J.CS,+p.H,XCSJ+pH
j)
(8.29)
I.J
,.factor
g,}
= 90 a'J{Au.
(8.30)
good estimate
for' it allows us to determine A.'J. Since the result is the difference bet. .n
two terms with the same order of magnitude the accuracy is usually low.
4.2. TENSOR: OPBRATOR
250
FINITE GROUPS
(eh. 8, 4
H = Eo+D[3S;S(S+ 1)]
(8.31)
where E and D are two constants. The next term would be the polynomial
or Y~ in ~ we require inversion symmetry. How high
equivalent of
a power of S is included depends on the number of levels, that is on the
total spin value, of the system we are describing. In general it can be stated that:
The number of invariant tensor operators necessary to describe a perturbation on a state of 2$' + 1 components is finite, since the total number of
independent Hermitian matrices is (2S+ 1)(S+ 1).
The generalization of the idea illustrated above is of particular importance
for the work in rare earth ions. In this case the spin orbit coupling is of such a
strength that Land S are not good quantum numbers and the electric field
will have the effect that the levels characterized by an orbital momentum J,
which has a degeneration 2J+ 1, will split into a certain number of groups
of levels. It_wQwd be impossible to calculate this by the previous perturbation
theory since in this case the L S coupling is not a small perturbation
compared to the electric field, but the rever~e is true. However, it is possible,
,although rather tedious, to take the field as a perturbation but since it acts
only ion the orbital part of J, it is first neeessary to decompose the J.
In imany problems, particularly if the components of the multiplet 1 are
far a~art, it is sufficient to give symmetry considerations and postpone the
de~imination of the constants involved.
Although the principle for such a treatment was already indicated by
wigner arid Kramers, the first practical evaluation was made by Stevens
*~o_,~cu1ated the operator polynomials corresponding to Yf, Y~,
as
well as the multiplying factors for the ground state of each of the rare earth
ions. The first results are indicated in Table 8.S.
Y:,
y2
TABLE
~(lzlr')
8.5
S (x1'(3J.:+J(J+ 1)]
:E(35z43orzs +3r&)
:E(231z431S"'z4105r' zlSr4')
i'''''[231J!315J(J+ 1)J:1735J~+ l05JS(J+ l)j;:;
525J(J+ 1)I:+294J:SJ8(J+ 1)3+40JZ(J+ 1)= 6OJ(J+ 1)1.
1
A multiplet is a group of leveis!' originating from the sarne Land S value. Tbe compo
nents are J
Ch. 8, 4]
OPERATOR HAMILTONIANS
251
0; =
SlG,S
(j = 1 ... h).
(8.33)
Since these operators are linear and since there are only a finite number of
different operators available then each operator generated in this way from a
given G f can be written as a finite sum of operators.
m
G;(j)
= L a(j)il G ,
m < h.
(8.34)
'=1
tonian:
(1) Operators that are invariant under the group t th.at corresponds to the
252
FINITE GROUPS
[eb. 8, 4
mea
fun
(8.35)
whetf1 A', B', and C' are constants, or actually functions of the radial
coor4inate.
owever, this is not real (Hermitian), hence ignoring the imaginary
part we find
(8.36)
for the coupling." Jbis result is rather obvious in this limple example, but
for more sophisticated symmetries group theory is needed in order to
construct the linear combinations of operators that transform like an
irreduciblo basis for a certain representation.
Now to, each irreducible representation of a certain dimensionality n
belonp another, such that the direct product of the bases functions generates
the unit representation, i.e. a sort of genera1ized internal product is taken as
in vector analy$ia and' an invariant is obtained. This adjoint set of basis
fUDCtions forms a space of the same dimensionality and it is also irreducible.
Ch..8, 14, 5]
XRAMEIlS' THBOIlEM
253
s.
Kramers indicated two proofs of his theorem. The first one (1930) is the
most.n~ and is base4. Qu. the properties of the coefficients of B and B
in the Hamiltoo.jan just mentioned. The second proof (1933) is less abstract
and has the adVasltage that it is ~ol, connected with actual calculations.
Suppose there is a single level characterized by J. The state vector is a linear
254
[Ch. 8, S
FINITE GROUPS
(8.37)
or in the Diracnotation:
<I
(8.37a)
= <JM)(MI.
Previous considerations have shown us that the matrix elements of the electrical potential are proportional to a ClebschGordan coefficient:
(J,
(8.38)
M, A.JlIJlJ
M').
(8.39)
2J+M+M'
= 2(J+M')+MM'.
(8.40)
The first t~rmQf this expressi9Jl j !llways even since if J is halfinteger, Mis
also halfinteger. Combh.UDS (8.38) and (8.39) gives the following symmetry
relation for the matrix elements:
(MIVIM')
= (l}M'M(M'IVIM).
(8.41)
= MgPBHz:
<MIW(H)IM') = ( 1)M1M(M'fW(H)IM)
(8.42)
as one can see n;adily from the equations above. The magt).eticfield behaves
under th~ transformation
. from M to  M' and M' to  M in "the opposite
..
way
the electric field. The secular equation for the coefficients (MI) are:
as
..
E(M'I)
==
L [(M'IVIM) + (M'IW(H)M)J(MI).
M
(8.43)
Ch. 8, 5]
255
KRAMERS' THEOREM
As a result of the properties (8.41) and (8.42) a second secular equation can be
formulated as follows:
E( l).l+JI<iM) =
I:
[(M'IVIM) + (M'I W( B)IM>](l).l+M(iM).
M
(8.M:
la)
= IM><Mla)
t~e
== IM><Mlb).
(S.4Sb)
(Mlb) = C( l)J+M<al_M).
(8.46)
(Mlb)
= C( _l)J+M< Mla)*
= c(Mla).
(8.47)
(8.48)
cc = (1) 2J C*C
(8.49)
FINrrB OROUPS
[eh. 8, $
H 
1
~
2m
e)a +etp+pHS.
( p+ A
c
(S.SO)
The operation "of A +  A and , + , . will leave the first term invariant,
but fielcI,Nvenalin the second term has to be accompanied by a reversal ,in
aiaD. of all thne ~pin components. The result of these considerations istbat the
equatioDS Of quantum mechanics will be invariant under time reversal plus
complex conjugation plus reversal of the sign of the spin components. Hence
Ch. 8, S]
KRAMBRS' THEOREM
257
it is stated that time reversal is equivalent to the applica1;ion of the last two.
. The operator which reverses the spin components is
(8.51)
Kramers calls this the spin conjugated spinor. This idea can easB.y\ be
extended to arbitrary spin values.
In dealing with a IISpin system product spaces can be easily constructed
from, and " and the corresponding operator will be a product of is,'., each
acting on one of the spins.
Having established the nparticle time reversal operator:
K := i"S~1)S~2) .. S~) C
(8.S2)
where C is the complexconjuption operator.
It is of course necessary to demand that udoublctimereversaltt be equiva1eat
to the unit transformation. If this operator is applied to a Doncieaenerate
wave function it is found that
(8.53)
henCe that the wave function would always vanish for odd values of n.
For even values of n time reversal corresponds to multiplication with a
phase factor
(8.54)
If ther~ is at least twofold degeneracy in the case of odd nvalues one may
have
(8.55)
Jt
" x p,+goS,
= Jl r",
(8.56)
11
(8.57)
258
[eb. 8, S
FINITE GROUPS
way
(t/ll' .$("'1)
(8.58}
("'2' Jtt/l2)
hence the trace of the two by two matrix is zero and the "center of gravity"
of the two corresponding levels will not shift from the zero field value as
long as we consider the terlns proportional to H:
\ (8.59)
E = Eo+.;It H.
th~
Ktf;' = 1/1'
(S.S4a)
which ~plies tllat the function is real. This idea can be generalized in case
the function is degenerate.
.
FROBENlUs and SCHUR [1906] have shown that there are in principle three
different kinds of representations possible for a finite group. The first kind of
rePreSentation consists of matrices that are real, or thatare equivalent to real
matrices. The second kind consists of matrices that are complex, but complex
insucili a way that the complex conjugate matrices vlill transform in a way
equivalent to the original. The third kind of representation consists of com..
plex, m.atriCes, . but the comple;x conjugate transformations belong to an
irreducible representation which is different from the original. It is clear that
thi .cllaracters of the representations of the first and the second kind are
r~, while the characters of the representation of the third kind are imaginab.ItfthefullrotationgrouprepresentationsofintegerJvaluehavethesame
prppertyas the representations of the first kind, while the representations of
t).tesecond kind correspond to the representations which have a halfinteger
{]' value. Since in the finite groups the distinction between the integer and half...
integer.values. ~f J.is lost, in. this case the distinction of the different "kinds"
of, representations has to be used.
The generalization of equation (8.54a) now is that all systems with an. ,
even number of electrons have representations of the first kind. The generalization of (8.55) is that all odd electron systems have representations of the
second kind.; The representations of the third kind are excluded since the
bilinear form
r
E=
L (1/1:, Ht/ln)
(8.60)
n=l
has to bean invariant and this excludes the possibility of such a representation.
259
JAHN..TELLER EFFECT
Ch. 8, 6]
6. JahnTeller Effect
6.1. INTR9PUCTION, EXAMPLES
In [1937] Jahn and Teller discovered the following interesting and useful
theorem: Unless a ~olecule is linear, stability and (orbital) degeneracy are
not possible simultaneously. The importance of this theorem is of cour~ that
certain configurations for molecules can be disqualified "a priori" and appli.
cations of this theorem are found in many places in the literature (see
bibliography).
In order to get an insight into the idea behind this theorem consider a
nuclear configuration that will have a certain symmetry which is maintained
if all distances are multiplied by a certain factor . This type of configuration
is called a similar configuration. In the case of vibrations, these similarity
vibrations are usually called breathing vibrations. Consider a configuration
with all the configurations similar to it and take the binding energy as a
function of the scale factor (or configuration coordinate). This function will
have a minimum, otherwise there is no possibility of obtaining a molecule
this way. Take the configuration coordinate corresponding to this minim1lD1
as a point of departure and study all other displaceIIJ.ent~ the'nuclei to see
whether they are stable or unstable.
Following Jahn and Teller, let us first give an example. Alineat triaiolDic
molecule can undergo vibrations in which the center atom is displaced
perpqndicu1ar to the cylindrical axis of symmetry. Sin~ the dis~lacc;Fetltd,
and ';d are identical, we wfiI have E(d) = E( d)$ To 'undets~hd'this
remdnber that the wave" function is characterized by' A =0, ~. 1, ~~2,' ...
(re~tively a tI, 1t, '6 etc. state) where ,1, measures th~'arilUl~t M~tiun
I
", : '
, :'
..
': "':"",}i,. ',"'"
around the zaxis, i.e. the cylindrical axis (comp~' Chapter 4,t1'4)~:The
states 1t and d, e~. are twofold degenerate, correspo1\ding: to right~;a.nU;,16ft
circU.lar orbits. A left circular motion stays a left circtitar modon.'whethertile
molecule is bent, straight or bent the opposite way_ Thffitst cgo~'bVef'lhto
the last if the molecule is rotated J80 around 'the z":ws, h~ll,~.:thewJiy~
function rotated over 180C> ,,ill undo this and since;lhe' energy, beihg~aa
expectation value, will not depend on the phase factor we should have
E(d) == E( d). This means that, assuming a. continuous energy curve, a
power series around the origin d = 0 will have only even terms, or that for
sm.all displacements this curve is a parabola. For A #:. o there are aetuaIJy
two parabolas,since the degeneracy \vas due to the cylindricaJ' symmetry
which js destroyed for d :1= o. (Figa 8$2.)
of
,~>'::
;',~"i,"
.>
260
FINITE GR.OUPS
o______
[Ch.. 8, 6
:d,
~J
_ _ _ _ _ _ _ _ _o
,
\
lEa
I
I
I
,,
I
/
"
."
J"
w.
(8.61)
find
<,
"
",:"'"
, "
, : '
,'/
""
tl!efottoWina scheme:
E 1 (+d) == E2 (d)
E2 (+d)  E1 (d)
(8. ,
(8.62b'
and
Ch. 8, 6]
lAHNTELLER. EFFBCf
261
part of the degeneracy which comes from the symmetry of the molecule will
be removed in such a way that one of the levels is lowered if the d :I: O.
Hence ~ deal with an unstable configuration. We want to stress tbatthis
example, and also the general theorem, shows that there is at least one type
of displacement which is unstable, and that this docs not exclude otlIer
displacements that are stable. As a matter of fact a stable diapJace~t has
already been postulated, the similarity displacement (or breathinavibration).
No need to say thAt one unstable displacement is aufficient to make the m0lecule go away from the initial configuration. This displacement is usually
referred to as a JahnTeller distortion.
V
~
DISPLACEMENT + d
............ d
,,
I
1
I
....<~
V
OISPLACEMENT  d
NOOEUNEal,
o
 00NOOEllNE 1
,
I
Fig: 8.3. Energy as a function of the displacement coordinate in a square molecule. The
nodelines refer to the nodes of the electronic wave function.
'6.2. NORMAL COORDINATES
In order to look into the general case it is nec;essary to makea sJisht digression into "normal coordip.ates" of vibrations in .mo~~ 'Ibil11I~
actually can also be consid~red as an appliaition of group theory, ap.d hence
is~ of interest on its own, but since this is a J)Utely classical subject it actually
falls outside the scope of this book. l TIle potential energy of a molecule under
nucle~_Jiisp1aCements
is
262
FINITE GROUPS
rCb. 8, 6
(8.63)
where qate the 3N coordinates of the nuclei measured from the equilibrium
positions (or any linear combination thereof) and b ,} represent either the
; apling CODIWlts in~:case the molecule is characterized by a set of masses
more
T =
LIi a'i4,4J ,
(8.64)
where the a'i are. dependent on the masses. The equations ofmotion obtained,
for instance, from the Lagrangian I (the Hamiltonian is just as good, but
associated with momenta instead of the q) are
L Q'Jii} + L bijqJ = O.
J
(8.65)
(8.66)
(which, as w~ will see ,below, is again a special case of (1.3a in order to
solve the problenfoy diagonalization. Multiply (8.65) by Cj and sum. over i.
This gives by comparing coefficients
L cia,) =
hj
and
LI cfbl} ==
AhJe
(8.67)
w~tb. the c, determined this way the original set of equations becomes:
..
(8.68)
Q+lQ == 0,
(0)2=:
A).
'.~
l'
o.
(8.69)
'
<
(aU 1 J the first term. will be diasonal. Solving the 8eCl11ar pr~blem will give a
set of:eipJ;ivaJues At and 'to e&cb. a set ofcoetlicients'4:f') which.iatum doter, Ir\'le.tart *ithNewtoo"s lawF == ma, and there is Ktually no eompoDhll reason to
use the Lagranaian formalism, the kinetic energy wiD eontain only diagonal torma.
Ch. 8, 6]
lAHN..TELLER EFFECT
263
Q}k) ==
L h~k)qJ
(8.70)
are the normal coordinates of the problem. Each of these coordinates vibrates independent of the other, with its own frequency and amplitude. 1his
amplitude is determined by the initial condition only. This result is applicable to a molecule but also to an infinite solid and leads in the last case
to the wellknown lattice waves, characterized by k, with their corresponding frequencies (J)(k).
The degeneracies in l are connected with thesymtrtetry of the molecule.
The same statements hold for solids where different kvalues mayeorre&pond
to the same t. The study of these degeneracies can apjn be undertaken by
group theory since they are the result of the fact that those transformations R
in laboratory space which are allowed by the symmetry of the molecule
(lattice) will induce a transformation in the normal coordinates. The result
of a transformation will be
a) if A is nondegenerate:
RQk
== Qk 1
(8.71)
b) if l is rfold degenerate:
,.
RQk
== l:aldQ,
(8.72)
1= 1
and/the coefficients (ale,) fonn an rdimensional representation of the symmiiry group. This representation will be irreducible, excluding accidental
degeneracy.
Take for example a triangular molecule in a twodimensional plane. The
number of actual degrees of freedom is 3 (i.e. 6 minus 2 translations minus
one rotation). One is the "breathing" vibration and the other two fonn a
degenerate pair~ called V2.( and vu(O) (HERZBERG, [194~], p. 84).. The
elements oft.be group (rotations of in around the center) transform one ~to
the other, or mto a linear combination of these two. This (real) twcrdimensional representation has nonsymmetrical matrices. It can of course be
symmetrized, but then the matrices will no longer be real.
1 Notice the differonce with quantum mecbanka where aU cootBcicnta are ;omplox
and aU matricea unitary" The only phase factor in this problem is :1:1.
264
[Ch. 8, 6
FINITE GROUPS
Normal.,.coordinates are used as a new system of axes in which the displacements of the molecule are described. In order to do this they have to be
normalized, and a positive direction has to be indicated for each of them,
If the magnitu~e of the normai displacement along the rth coordinate is
called '1r, the deformed molecule has cooi~inates,
(8.73)
where QO refers to the normal cpordinate representing the original shape of
the molecule (the corr~nding vibration is the breathing. vibration) and flo
is the scale factor and has the value corresponding to a minimum of the
energy. The Hamiltonian is a function of these t1, and close to equilibrium
(i.e. the equilibrium of the QO coordinate) it may be expanded as follows:
H
= Ho+ V
= Ho+
(8.74)
(n, m = 1 ... p)
(8.75)
and the
first order correction on the energy is found after diagonalization
of
!
'
this matrix
(8.76)
IThe energy is a scalar, i.e. has to transform like the unit representation.
If the matrix elements (8.75) are studied they transform according to:
r",.,xr,xr", = Lair;
(8.77)
are
Ch. 8, 6]
JAHN..TELLER EFFEcr
265
in the energy. The main part of the JahnTeller proof consists in showing
that for all nonlinear molecules, the direct product (8.77) contains the unit
representation.
Again take the example of a twodimensional square molecule. There are
8  3 = 5 vibrations possible. That is the breathing or totally symmetrical
one, plus 2 nondegenerate (called B tg and B 2g ) and one 2fold degenerate
vibration called Eu (Compare HERZBERG [1945], p. 92.) The wave fun'ction
can belong to one of the five representations of this group. (Compare
BETHE [1929] or HERZFELDMEIJER [1961]) but only one is degenerate
1"4 = E. Multiplying [r4 ]2 by B 2g we find that it contains r 1 == A g (The
same holds for BIg). Hence these two modes lead to decomposition of the
molecule, or at least to a nonsquare distortion.
How mu~h the molecule deforms depends on the actual shape of the
potential curves in Fig. 8.3. It may, for instance, be that the curves will go
through a minimum and increase again as suggested by the dotted part.
The distance from this minimum to the origin is the final amount of distortion. This distance may range from infinite, in which case the molecule will
dissociate along this mode, to very small. In the last case the effect may not
be detectable. This means that the application of the theorem has to be
accompanied by an order of magnitude calculation. The theorem also holds
for spindegeneracy, a statement that brings up some interesting details,
but Teller (See JAHN [1938]) estimated that the order of magnitude of the
dist~nce frOln the origins is so small that the implications are not important .
PROBLEMS
1~
= elS
or
eigenvalues.
f(r)
(2Y; + 2YJ+iY8),
==
l/I(x+a)
tation .
267
268
PROBLEMS
3. 1. Determine from the group table of the symmetry group .93 the
minimum number of eielnents necessary to generate the complete
:~roup.
3. 2. Make a group table similar to the example in Ch. III~ 2 for the
tetrahedral group. A geometrical representation of this group is
found "by taking the four points (1, 1, 1); (1, 1" 1);
(1,1, l)and( 1, 1, 1) in three dimensional space and performing
all spacial rotations that bring these points into coincidence. Is
this group the same abstractgroup as .9'41
3. 3. The ordinary complex numbers are a special case of hypercomplex
numbers. The basis of this algebra is related to the Abelian group
of order four. The hypercomplex numbers are
A 1 A=E,
A 1 B=A, A1C=F,
A 10 = C and A 1 F = D.
3. 5.. Obtain from the regular representation of ~5P3, as constructed in
problem 4, the two dimensional irreducible representation by
means of the projection operators. The character table is given in
12.
'3. 6~ Show that the orthogonality relations (3.16), (3.17) and (3.18) are
fulfilled for the example given in 7.4.
3. 7. It is stated in 11.2 that the matrix elements ail,
are linearly
independent, i.e. the form
a;t
3., ~:
jl
,UY
is only equal to zero if all A, ;! ... are zero. Show that this is correct.
The matrix 1 is independent of the operation D. (Hint: multiply by
a:!") and sum over a.)
Calculate the characters of a regular representation and show with
the help of (3.23) ,that the regular representation cQntains every
irreducible representation as many times as the dimensionality of
that irreducible representation.
269
PROBLEMS
3. 9. The 24 operations that bring a cube to finalpositions.i.adistinguishable from the initial positions form. a group_ This group is isomorphic
with the permutation group of four objects (the body diagon.a1s,
e.g. we number the corners such that two opposite corners carry the
same label). The symmetries of a tetrahedron.imhedded in, the cube
(compare Fig. 7.1) correspond to the elements of a subgroup of the
cubical group. Establish the correspond,ing permutations. Does this.
set of permutations form a symmetric group of lower order?
1
Drawing by Steinberg;
3./ 10. A cube in the conventional sense need not to have cubical SymDletry
(compare Fig. 3P.l), conversely there are objects that do not look
like a cube, and have the cubical symmetry. To find examples,
check through. the literature: WignerSeitz Unitce11 for b.c.c. alld
f.c.c.lattices (compare KrrrEL (1957], p. 286). Brillouin zones and
Fermi surfaces for cubic lattices. (Compare H.AItlUSON" [1960].)
3. 11. Let any two numbers a and b be equivalent in m  n == 4K where K
is some integer. Under this equivalence any number is equivalent
to either K = 1, 2, 3, or 4. Notation
m == n (mod 4).
(This is pronounced m is equal to 11 modulo 4.) Show that the
numbers 1,2,3,4 form. an additive group by constructing the group
table of the group. How many classes does this group have1
210
3.
PR.OBLEMS
12~
(CompareCh.m7.S.)Ifthebilinearformisindicated by F(x.I)
and the transformed version (Ax Ax) by P<C), show that
I=
L F()
IJ
is invariant under the operations of the set. If a linear transformation 1 is introduced that brings .1 into the diagonal form, th~ new
set of coordinates form the basis for a unitary representation of the
set ofm.strices. Show this and apply this procedure for "unitarisation" to the example (lfthe two dimensional representation in 7.4.
J.. 13a.. Perfornt the reduction of the regular representation ofthe group sP 3
~ith the help of the Young tableaux. The three tableaux will be
labelled H (for horizontal), L (for I~shaped) and V (for vertical).
Show that PQ for the tirst and last is equal to the group itself and
that PQ for the Ltableau consists of four elements.
Show that p :..:: 6 (for H and V) and p = 3 for L.
3" 13'b. lJse the representation reSUlting from the basis t1, e2' 63 as discussed in 7.4 to calculate the ptojection operators corresponding
to the following tableaux:
1
2.
271
PROBLEMS
e,
(,  itT )* ( ~ ~ i11) =
fl.)
+, {X*) 2 + (P_.+ 22
. 2
~...
272
PROBLEMS
5. 4. The Wigner coefficients can be considered asa matrix which connects QJtf with qM",.qrnc. Calculate this matrix for
T;
SYMBOLS
V2
with . . is associated
transforms as
functional scalar product
(time) average, also: expectation value average over probability density function
direct product of matrices or sets of matrices
addition of representation
small, socalled "virtual", v~on of x.
vector in ndimensional space
base vector of a vector space
vector space spanned by 11 basis vectors
Kronecker symbol (equals 1 if i == k, and is zero otherwise)
Matrix consisting of elemeDts
Inverse of A that is A1 A == I
Unit matrix I !II (6 11)
Unitary matrix used for similarity transformation
Metric tensor
Complex conjupte vector, matrix
transposed vector, niatrix
Hermitian conjupte matrix (i.e., complex conjugate and
transposed)
Operator
Adjoint operator
Domain of intearation
Fourier component or generalized Fourier component
Dirac delta function
02
a2 02
"Delsquared'  +  + 
velocity of
(m1
1m)
Bravector
K.etvector
frequency
(.)
<>
x
+
bX
%
e,
illS
~fl
A = (ali)
AI
I
$, U
(g",)
x,A~
... .....
x,A
At
A,a
A
D
p", l't
d(XIX2)
or
ar
liaht
213
OZ2
274
SYMBOLS
= 2n:v
(J)
k
h, h
,,;'
angular frequency
wave (number) vector; k = 271/A
. . h of Planck, h = h/2rc
\c
rnOlnentuxu vector
tJi, 4'
wave function
volume element of configuration space
~
energy eigen value, (occasionally also used for electric field
strength)
Hamilton operator
potential energy
an~r DnounentUnl vector or vectoroperator
perturbing energy
perturbation parameter
set of unperturbed eigenfunctions
auxiliary parameter in nearly degenerate systems, expressing
d't
E
H
V
L,l
AW
A
n, 1, m
P,
s~ .<.~
E
~,
,9'"
.;Ie
~S!I,.
s4 3
E, A,/B
CI:
c.~
..(A)
X(i)(C)
f'
acter~'t
Xi = Y hilg ~(Ci)
number of elelnents in class i
...
1:
<; or \'
C;
e(p.)
hypercolnplex number
i .. th (irreducible) representation
SYMBOLS
275
~d:z!':l
{ 13J]
Wigner 6jsymbol
t 1, t 2, t3}
a, b, c
T
(TIR)
a*, b*, c*
276
k
uCr)
I
8.
,.
K
.I
'I,
Q,
D
II
SYMBOLS
r.
References cited
Abrapm, A. and M.H.L. Pryce, 1951. Proc. Roy. Soc. A 230 169
,
Bethe, H. A., Ann. Phys. (~J 3 (1929) 133 or [Consultants Bureau (EDaJith Translation)
New York]
Birkhoff, 0., 1950, Hydrody1lllmiC8 (Princeton University Press, 1950; Dover Publicatioas.
New York, 1955)
Born, M. and P. Iordan. 1930. Elemelltare QlIII1ltSII Mecltaalk (Spriaaer, BerUn)
Boucbert. L P., R. Smoluchowski and B. P. Wlpler, Phys. Rev. SO(ll~ 58 Brinkman. H. C . 1956. Applications ofSpi1tO' InWU'iants In Atomic PlqJQ (North Holland
Publishing Co.. Amsterdam)
Burc;khardt, 1. J., 1947, Die Bewegungsgruppen tIer KrUIIIIIo.,.". (BirkhIuser, Basel)
Cattan, E., 1938, ie~ons sur Ia Ii/oris dtts SpiMIUS (Hermann ot Cfe., Peril)
Canan, E., 1894, Concernin8 tlte 8tructure 01 finite tmd COlltl1ll10118 #tl.flS/orm4t1on. grt1f1J16
(Thais N~y. 1894)
Canan, E .. , 1913, BuB. Soc. Math. de Franco 4 53
Cartan. E., 1914, Journal de Math6matiques 10 149
Cayley, A., 1854. Phil. Mag., vii (4), 4057
Condon, E. V. and G.JI. Shortly, 1935, The TM01'Jl ofAtomic Spttctrtl (Cambriclle U.mw.
~n'
Press)  
.'
Dirac, P. A. M., 19S8, The Principles of Qllan/urn MecIuznlcs,4th ode (Clarenclon .....
Oxford)
Umv..a,
Rl
. ,
Springer)
Jahn, H. A. and E. Teller, 1937, Proc. Roy. Soc. (London) A 161 220
lahn, H. A." 1938, Proc. Roy. Soc. (London) 164 117
IGttel, C., 19;57, Introduction to Solid Sl~e P/tJ1SIC3, 2nd eel. (Wiley, New York)
Korringa, I., 1954, Tecl1n. Rep. (Ohio State University) aDd Solid State Physics (to be
published)
271
278
REFERENCES CITED
"
York)
f:
SYSTEMATIC BmUOGRAPHY
1 .MATRICES AND LINEAR VECfOR SPACES
Al.BD.T, A. A., 1956, Fundamentlll Concepts 0/ Higher Algebra (University ofChicqo
Press), (Chapter 'I Groupa, 'Chapter RI< Vector Spacea a.ad Matrices)
BODBWlG, E. t 1956, Matrix Calclllus (North Holland PublisJaial Co., AmJterdam)
HAUfOS, P. B.., 1958, Flnit~DI~l Vector SptlCU (Van Nostrand. PriDcetoa)
MAllGENAU, H. and O. M. MURPHY, 1943, The Malhemotics 01 Phyric6 a1IIl Clttlmbtry
(Van Noatrand,New"Yotk), (Chaplet 10 Matricea'and Chapter IS Group TIMory)
VAN DBa W ADDIlN, B. L. t 1949, Modern A.lgebra (FftJ:derick Uupr, New York)
<
2. QUANTUM MECHANICS
",,~'
3. 'GROUPS
.BoERNE&, H., 19S?,D~stellung,nvoll GI'UP~. mit BerllC/uicltligll1J.dRlledII(I,*tk,
. inoilir,ji"'PJ.ystk (SJ)riDger, Berlin) ( Rtpresentatlon,'oj' GroUps: :w1tll spM:IM CIJ~''''''''
for IM".,Is of Alodern Physics (transla~d froI9 German by P. G. Murphy et 01.)
279
280
SYSTBMATIC BIBUOGItAPHY
3.1. Tableaux
.. ~
"',plil
London)
MELVIN, M.
tion)
s.
R.OTATIONS IN SPACB
SYSTEMATIC BIBLIOGRAPHY
281
CoNDON,
0/ AngultV AI""..",,,,,,
(AddisonWesloy. Cambridge, Mass.)
ROSE, M. B., 1951, Elementary Theory of Angular Momentum (WHey & Sons, New York)
S.I. Spinors
BlUNDtAN, H. c.., 19S6, ApplicatJolfS of SpilfOl' Invariant' in Atomic Phyric6 (NorthHolland
Publishing Co., Amsterdam)
E., 1938, Le~ons sur la thsorle des SpinelUs (Hermann & Cio, Paris)
CARTAN"
6.1. Tables
L. C" 195~ Tables 0/ R.caIa eoeJjkients (Oak Ridge Natienal Laboratel'J,;
Physica Div., ORNLlSOl, suppl. 1, Febr. 1952)
8JJI>lblIUdlNt L. C, J. M. BUIT and M. B. ROE, 1952, Revs. Mod. Phys. 24249 (T'heIe
tables aive W(abcd; eI) for e :i 2 and abcd/ arbitrary)
CoNDON, E. V. and G. H. SHORTLY, 1935, The Theory 01 Atomic Spectra (Cambtidae
University Press)
BDM9NDS. A. R", 1957, Angular Momentum in Quantum Mechanics (Princeton Uaivenity
~, New Jersey)
ROTlNBEllG. M., R. BIVINS, N. MImlOPOLII and J. K.. WOOI'BN, 1960, The 3} aDd f,.,)
I~bols (Wiley & SoDS, New York)
BlBDENJIA.llN,
BA.Rms, R.. B.t R. R.. BttATI'AIN and F. SElTZ, 1935. Phys. Rev. 41 582
BaLL, D., 1954, Rev. MOd. PhyS. 26 311
.BOU<XABlt.Tt L P., R.. SMOLUCROWSICI and S .. P. WXGNBR., 1936, P1;1ys. Rev.. 50 58
BRILLOUIN, L., 1953, Wave Propagation in Periodic Structure8 (Dover Pubuc.tioas.
New York)
,
BRAVAIS, A., 18S0, On the systems!ormed by poilUS Nlg1llarly dlstri6ated Oil 4Jl_~O!, 11)41
space (Ens transl. 1949 by tho Crystallography Society of America, Ho\lltoJl, TexaS>
BUllCKHAllDT, J. J . , 1947, Die Bewegungsgruppen der Kr"'tallog'aplt~ (Blrkhl\JS6r, Buef)
DAVYDOV, A. S., 1951, TMory of Molecular ExcilolU (Translated by M. Kasha and
M. Oppenheimer, 1962) (McGrawHill, New York)
ELLIOTT, R. J., 19S4, Phys. Rev. 9Ci 280
JOHNSTON, D. F., 1960, Rep. Progress Physics 23 66
10NESt H." 1960, The Theory 0/ Brillouin ZOllftS and Electronic States In Crystau (North..
Holland Publishing Co., Amsterdam)
HERMAN, F~!l J958,. Rev. Mod. Phys. 30 102
lIERRJNG, (~." !937~ Phys. Rev. 51 365
282
SYSTEMATIC BIBLIOGRAPHY
7.2. Tables
Inlernaliolllli Tables for XRay Crystallography 1952 (Eng. Kynoch Pross, Birmingham)
cH., J. WALTER and O. KIMBALL, 1944, Quantum Chemistry (Wiley & Sons.
New York)
W., 1928, Z. f. Physik 47 835
HEITLER, W. and G. ReMER!! 1931. Z. f. Physik 68 12
MULLIKEN. R. S., 1933, PhY:3, ReTll A~3 279
BEITLER,
SYSTEMA'TIC BIBLIOGRAPHY
283
.J
(llermann , Paris)
MA~ F . 1961, Gruppenth~orie der Eigeruchw;ngungen von PlUtktaysteme (Springer,
Berlin)
WILSON, E. B.,
INDEX
Affine. 1
Analos

Buler, 191
fixed.40

main, 11, SO
of' quantization, 249
lee also Hoisenberg, Scbr6dinaer
mot.Uie. 208
Bloch theorem, 217
Bra. He unit, vectors
Bfavail lattic:ca. .. 223
Brillouin zone(s). 54, 213. 219
CoIl 1
 coklventional unit. 206
 w;ilt 213
cu.,8cter(s), 86
~ ).,f ,opat&,
98
 of a representation, 8S
 primitive, 86
 tables, 9S, 97, 98
 thoory of, 99
Clua (c1uaes), 67, 98. 101
 function of, 8'
 Dumber of, 87
of permutations, 11
 Racah, 193
 structure, 94, 95. 98
 Wiper, 181
Combination
 linear. of atomic. orbitals, 209
Commutative operations, 62
Commutator, 139, 140
Commute, 14
Component8. lee spectral
Conditions
 integrability, 139
 periociicooundary, 211
Confiauration
 space, 34, 35. 110
 unstable, 261
Congruency. 69
Conjugated, transformations
Conjugation, 221
 complex, 2S6
Conventional unit cell, 206
Convergence, 21
Coordinates
 homogeneous, 133
 normal, 261
Correspoft<ience
 onetoone, 61
Coset, 65, 222
 left, 65
Couplinl
 between levels, 53
 RusseUSaundon, 161
 spinorbit, 190, 246
Cross over, 54
Cycle (cycles), 70
 notation with, 100
 order of, 70
Darstellung, 74
Decomposition, 76
Degeneiacy, 23. 235
 accidental, 224, 264
_ .. essential, 55, 119, 223
 exchange, 59, 120
 quasi, 49, 5S
Determinant
 secular, 239
 sum of a, 94, 95
Qaaical waves, lee waves
Oebach.;Qordan
 coefticiont(s), 181, 190
 formul~ 152
 series, 181
Coeftlcient(s), 8ee Fowier
 QebschGordan. 181, 190
284
285
INDEX
DlasonaUzation, 264
Dirac delta tunction, 24
Divisor
 normal.. 67
Doublet(s)
 Kramers, 2S3, 257
Bffect(s)
 lYlomaanetic, IS7
 PaschenBack, 172
 Stark, 167
 Zeeman, 156, 168, 183
Eigonfunctiona, 21, 32
 symmetry adapted, 233
Eipnvalues, 21, 32
 dqone.rate, 1J3
 spectrum of, 22
Eiaenvectora. 21, 175
Bloment(s)
 complex or, 65
 diagonal, 105
 idempotent, 97, 98
 of tho space group, 202
 reduced matrix, 192
 screw, . 202
 unit, 203
Energy splittina, 245
Equation
 Scb.rOdinaer, 33, 110
 secular, 51
~t, 8ft also transformation, " 74
Euclidean, 7
Euler, 1M anal.
.
square iDtearablo, 17
Goldenrulo, 47
Group
 Abelian, 62, 121, 167, 204, 207

abstract, 241
additive, 62
additive submitted to a system of 0perators, 63
ackUtivo'with IIlwtipIlcaton, 63
alaebra. 88
continuous, 138
crystalliDe point, 198
cubical, 234
cyclic, 64
double, 241
factor, 68, 222
full rotatio~ 198
homomorphic, 72
permutation, 100; 110
point. 199, 228
postulates, 61
rotation(I), 110, 133, 142
space, 88, 92, 206
symmetric. symmetry, 60, lOS
table, 63
Pactor
 Land6, 6, 149, 171, 249
 phase, 38
Field
 electric, 254
 mapetic, 254
Form
 bilinoar, 8, 21, 258
 box, 99, 115
 diaaonal, 11
 Hermitian. 80
 quadratic, 9
Fourier
 coefDcients, 18
 expansion, 41
 series, 24
Function(s)
 anaular wave. 240
Bloch, 218
free electron wave, 218
fundamental basis, 17
of a claaa, 86
ortho,onal, 92
Hamiltonian
 spin, 248
Harmomc(a)
 spherical, 184, 190, 239
Hoisenberl
 axes, 42
 matrices, 43
 representation, 42
Hermitian. 9, 40
 fol'lD, 80
 matrix, 11
 operator, 21. 22, 37, 40
Hilbert apace, 41
 rays of, sell ray
Holohedra1 isomorphism, 72
Homomorphic
286
INDEX
 groups, 72
 matrices, 97
Hund9 s rules, 246
Idempotent (s), 102
 elements, 97
 essential, 103
 induced.. by, 105
Identity, 60, 61
Intensity, 30
Interaction(s)
 strong, 166
 weak, 166
Invariant(s), 112
 operator, 251
Inverso(a),inW1'lioa. 60, 62, 64, 164
Irreducible representations, see lOPresen..
tations
 system of, 83
Isomorphic, 72
 connection, 74
 matrices, 97
Isomorphism, 83, 84
 holohedral, 72
 merohedral, 72
Ket, see also unit, vectors
 projected, 10
Kra11leIS doublets, 253, 257
Land6, see factor
Laporte, rule of, 165
Latti~(s)
 lJravais, 223
,Inverse or reciprocal, 213, 218'
utw, associative, 62, 204
Legendre, see polynomials
Length, 6
 of a vector, 28, 80
Linearly independent, 1
Little group
 of the first kind, 222
 of the se.cond kind, 221
Mappings, 75, 82, 88
Matrjx (~trices)
 adjo"int, 8
 diagonal, 99
 Heisenberg, 43
. !fermitian.. 1 J, 144
. hcilllomorphic, 97
~ inverse, 4
isomorphic, 97
mapping, 2
mechanics, 15
Pauli, 144
projection, 64
rectangular, 82
 secular, 50, 264
 stepwise, 14, 85
 sumofaclass, 9S
 transformation, see 1lI80 transforma...
tion, 1
 unit, 2
 unitary, 11, 20
Metric, 6
Moment
 magnetic, 257
Monomials, 173, 178
MUltiplet(s), 161, 250
Multiplication rule, 3
Multiplicators, see group, additive
Nonholonomic, 140
Norm, 6, 16
 of a vector, 28
Notation
 with cycles, 100
Numbers
 hypercomplex, 88, 103, lOS, 106
 rational, 62
Observable. 32, 38
 physical, 40
Octahedron, 201
Operations
 from the right to the left, 71
 the P.Q, 162
Operator(s), 3, 61
 Hermitian, see Hermitian
 irreducible tensor, 184
 linear, 19, 3.7
 nuclear spin, 252
 projection.. 94, 97, 99, 104, 237
 time reversal, 257
 see also angular momentum
Orbit, 221
Orbital motion
 "frozen inu, 246
Ctrders 62
 of a cycle, 70
Orthogonal, see vectors
Orthogonality relations, 89, 91
Orthonormal, 17
287
INDEX
Orthononnality
 of character systems, 100
Parameter kroup
unitary
three, 131
Parity, 164
Parseval, formula of, 19
Partitio numerorum, 101
PaschenBack etrect, 172
Pauli principle, 106
Permutation (permutations), 59, 221
 class of, 71

cyclical, 101
even or odd, 71
group, 100
 product of two, 60
Perturbation theory, 47
Polynomials
 independent, 18S
 orthogonal, 18S
 Legendre, 185
Primitiv~ see character
Principle, complementarity, 31
Probability, 39
Product, 203
 antisymmetrical, 189
 direct, 151
 of two groups, 206
 scalar, 7, 16, 28
 semidirect, 207, 242
 weak direct, 207
Projection, 88
 even odd, 102
 operators, 97
 stereographic, 132
Quadratic form, 9
Quantity, physical, 40
Quantum mechanical waves, see waves
Racah coefficient, 193
Ray(s), of the function space, 38
Reduction, comp1ete, 76
Reflection (s), 124, 203
Relation(s), orthogonality, 89, 91
 commutation, 186
 compatibility, 225
Representation, 74
 double valued, 137
 equivalent, 74, 85
 faithful, 74, 137
 identity, 74
irreducible, 7S,
77~
89,
91~
alternati11l, 89
nonequivalent irreducible, 87
of the first kind, 2S8
of the second kind, 252, 258
of the third kind, 2S8
product, 193
reducible, 234
  regular, 88, 89, 96, 104
Rotations, 203
 infinitesimal, 137, 174
 plane, 122
Rule(s)
 golden, 47
 Hund's 246
 triangular, 240
RussellSaunders coupling, 161
configuration, 136
function, 15
group, 92
product, 159
 representation, 74
 spinor, 136
 unitary, 7
Spectral components, 30
Spectrum, see eigenvalues
Spmor(s), 136, 158, 241
288
INDEX
 normal, 220,' ~
Subspaee", 14" ,111

factor, 76
irreducible, 170
Substitutions
 linear, 140
Sum. or sq~J 23
Symbol
 3J, 181
Symmotry __
128
SyatcIn
Theorem
Blocb. .. 217
l'
Tnu.ladon(s)
 primitive)" 210.
putC, 2ll
TraDJ~ inverse,
Trl.DlP6iitionll 70
Transformation

C&ll()Dical, S
corUuaa~ 67
oquivalent, 67
induced, 111
Uniqueness, theorem, 81
Unit
 bra, 10
 element, 60
 ket, 10
Unitary space, 7
 and unimodular group, 131, 152
 matrix, 11. 20
 representations, 80
 transformation, 8
 see also parametersroup
in~iant,'f 75
 spherical,
vectors, 212
 axial, 164 basis. 1, ISO
 braunit, 9
 in tho sroup space, 88
 tetunit, 9
 null, 82, 135
 of the twodimlDlional space, 136

orthogonal, 92
orthogonal basis, 28
orthoaonal unit. 7
primitive translation, 202
reduced, 222
reduced wave, 218
unit, 1
wave~
29
Wave(s)
 "cl#sSica1. 29
fu.1lctiOD,
38
 monochromatic, 31
. packet, 30
Wigncr