University of Connecticut

DigitalCommons@UConn
Chemistry Education Materials Department of Chemistry
10-9-2007
Introductory Mathematics for Quantum
Chemistry
Carl W. David
University of Connecticut, Carl.David@uconn.edu
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Recommended Citation
David, Carl W., "Introductory Mathematics for Quantum Chemistry" (2007). Chemistry Education Materials. Paper 50.
http://digitalcommons.uconn.edu/chem_educ/50
Introductory Mathematics for Quantum Chemistry
C. W. David
Department of Chemistry
University of Connecticut
Storrs, Connecticut 06269-3060
(Dated: October 9, 2007)
I. SYNOPSIS
Since much of the mathematics needed for quantum
chemistry is not covered in the rst two years of calculus,
a short introduction to those methods is presented here.
Elegance has been eschewed in the Einstein spirit.
II. ORTHOGONAL FUNCTIONS
A. Dirac Notation
The notation employed in beginning discussions of
quantum chemistry becomes cumbersome when the com-
plexity of problems increase and the need to see struc-
ture in equations dominates. Dirac introduced a notation
which eliminates the ever-redundant from discourse.
He dened a wave function as a ket.
The ket is dened as |index > , where index is
some human chosen index or indicator whose purpose is
to label the state (or the function) under discussion. For
a particle in a box, a potential ket is

n
(x) = |n > N
n
sin
_
nx
L
_
=
_
2
L
sin
_
nx
L
_
(2.1)
where the domain is 0 x L, N
n
is a normalization
constant, and n is a quantum number, i.e., an index
chosen by us.
For the hydrogen atom, an appropriate ket might be

n=3,=1,m

=1
(, , ) = |3, 1, 1 >= N
3,1,1
(4 )e

sin e

(2.2)
which is a 3p electrons state () is a dimensionless radius.
A harmonic oscillator might have an appropriate ket
of the form

3
(x) = |3 >= N
3
_
8
3
x
3
12x
_
e

2
x
2
/2
(2.3)
i.e., the ket notation allows us to indicate inside the
funny delimiters the essential characteristics of the in-
volved wavefunction without extraneous elements which
might distract attention from the overall viewpoint being
propounded!
B. The Dot Product
Returning to the hydrogen atom, the following vector
< 3, 1, 1| = N
3,1,1
(4 )e

sin e
+
(2.4)
which is the complex conjugate of the original wave func-
tion [1] , is known as a bra vector, and the notation
< 3, 1, 1|3, 1, 1 >= 1 (2.5)
is a shorthand for
_
all space

3,1,1

3,1,1
d = 1 (2.6)
(i.e., the normalization equation, required so that the
probability of nding the electron somewhere is 1, cer-
tain(!)), which itself is shorthand for the complicated
three-dimensional integral, usually display is spherical
polar coordinates.
One sees that constructing the braket [2] consists of
two separate concepts, making the bra from the ket
by using the complex conjugate, juxtaposing the two in
the proper order, and integrating over the appropriate
domain. The analogy of this process is the dot product
of elementary vector calculus, and it is here where we get
our mental images of the processes described.
In three space, x, y, and z, we have unit vectors

i,

j,

k,
so that an arbitrary vector as:

R
1
= X

i +Y

j +Z

k
could be re-written as
|R
1
>= X|i > +Y |j > +Z|k >
In this space, one doesnt integrate over all space, one
adds up over all components, thus
< R
1
|R
1
>=

R
1

R
1
= X
2
+Y
2
+Z
2
since |i > is orthogonal (perpendicular) to |j > and
|k >, etc..
Typeset by REVT
E
X
2
In the same sense,
|arb >=

n
c
n
_
2
L
sin
_
nx
L
_
(2.7)
where |arb > is an arbitrary state. This is our normal
entry point for Fourier Series.
Before we go there, let us re-introduce orthogonality,
i.e.,
< n|m >= 0 =
_
domain

m
d ; m = n (2.8)
where the domain is problem specic, as is the volume
element d. This orthogonality is the analog of the idea
that

j = 0
as an example in normal vector calculus.
III. FOURIER SERIES
A. Particle in a Box vis-a-vis Fourier Series
The normal introduction to orthogonal functions is via
Fourier Series, but in the context of quantum chemistry,
we can re-phrase that into the Particle in a Box solution
to the Schrodinger Equation, i.e.,

h
2
2m

x
2
+ 0 = E (3.1)
in the box (domain) 0 x L. The solutions are known
to be

n
(x) =
_
2
L
sin
nx
L
= |n > (3.2)
where n is an integer greater than zero, and L remains
the size of the box.
Now, a Fourier Series is an expansion of a function
(periodic) over the same (repeated) domain as above, in
the form
|function >=

i
c
i
|i >=

i
c
i
_
2
L
sin
ix
L
(3.3)
(where we changed index for no particular reason from
n to i, other than to remind you that the index is a
dummy variable). The question is, what is the optimal,
best, nicest, etc., etc., etc., value for each of the c
i
in this
expansion?
B. A Minimum Error Approximation
To answer this question, we look for a measure of error
between the function and the expansion. To do this we
dene a truncated expansion:
S
m
=
i=m

i=0
c
i
_
2
L
sin
ix
L
(3.4)
where, contrary to the particle in a box, we have em-
ployed the i=0 particle in a box basis function. Now, we
form an error at the point x:
|function > S
m
(x) = err(x) (3.5)
and notice that if we added up this error for every value
of x in the domain 0 x L we would be approaching
the concept we desire, a measure of the error, the dif-
ference between the function and its approximation, the
truncated series.
But, you say, sometimes the error (err(x)) is positive,
and sometimes its negative, depending on circumstances.
We want a measure which counts either eect properly,
and the answer is to dene a new error
(|function > S
m
(x))
2
= ERR(x) [err(x)]
2
(3.6)
where clearly, the l.h.s. is positive denite, and therefore
can not give rise to fortuitous cancelation.
S (x)
m
x
|function>
0 L
ERR(x)
ERR(x)
ERR (x)
2
domain
FIG. 1: Error involved in approximating a function.
So, adding up ERR(x) at each point x in the domain,
we have
_
L
0
(|function > S
m
(x))
2
dx =
_
L
0
ERR(x)dx ERROR
m
(3.7)
3
ERROR
m
is now a postive denite number which mea-
sures the error committed in truncating the approximate
series at m. We re-write this explicitly to show that sum-
mation:
_
L
0
_
|function >
m

i=0
c
i
_
2
L
sin
ix
L
_
2
dx =
_
L
0
ERR(x)dx ERROR
m
(3.8)
and form the partial
ERROR
m
c
j
(3.9)
holding all other c
i
constant, where i = 0...j...m, which
is
ERROR
m
j
= 2
_
_
L
0
_
|function >
m

i=0
c
i
_
2
L
sin
ix
L
_
_
2
L
sin
j
L
dx
_
(3.10)
which we set equal to zero. This means that we are searching for that value of c
j
which makes the ERROR an
extremum (of course, we want a minimum). This leads to the equation
_
L
0
_
|function >
_
sin
jx
L
__
dx =
_
L
0
__
m

i=0
c
i
_
2
L
sin
ix
L
_
sin
jx
L
_
dx (3.11)
and, since one can exchange summation and integration, one has
_
L
0
|function >
_
sin
jx
L
_
dx =
m

i=0
_
L
0
_
c
i
_
2
L
sin
ix
L
_
sin
jx
L
dx (3.12)
But the right hand side of this equation simplies because the sines are orthogonal to each other over this domain,
so the r.h.s. becomes
_
L
0
|function >
_
sin
jx
L
_
dx = c
j
_
L
0
_
_
2
L
sin
jx
L
_
sin
jx
L
dx (3.13)
since the only survivor on the r.h.s. is the i = j term.
c
j
=
_
L
0
|function >
_
sin
jx
L
_
dx
_
L
0
__
2
L
sin
jx
L
_
sin
jx
L
dx
(3.14)
Multiplying top and bottom by
_
2/L one has
c
j
=
< function|j >
< j|j >
(3.15)
which is fairly cute in its compactness. Of course, if |j >
is normalized (as it is in our example) then
c
j
=< function|j > (3.16)
which is even more compact!
C. Completeness
What if we wanted to approximate a function of the
form
sin
7x
L
(3.17)
and i=7 were omitted from the summations (Equation
3.3), i.e., the summation ran past this particular har-
monic. It would look like:
+c
6
sin
6x
L
+c
8
sin
8x
L
+
Clearly, since each sine is orthogonal to every other
sine, the seventh sine
_
sin
7x
L
_
would have no expansion
in this series, i.e., each c
i
would be zero! We can not
4
leave out any term in the series, i.e., it must be complete,
before one can assert that one can expand any function
in terms of these sines (and cosines, if need be). Said
another way,
sin
7x
L
= c
0
+c
1
sin
1x
L
+c
2
sin
2x
L
+
since the one term on the r.h.s which is needed, was, by
assumption, absent!
IV. LADDER OPERATORS
A. Laddering in the Space of the Particle in a Box
We start by remembering the trigonometric denition
of the sine of the sum of two angles, i.e.,
sin( +) = sin cos + cos sin (4.1)
We seek an operator, M
+
which takes a state |n > and
ladders it up to the next state, i.e., |n+1 >. Symbolically,
we dene the operator through the statement
M
+
|n >|n + 1 > (4.2)
and we will require the inverse, i.e.,
M

|n >|n 1 > (4.3)

where the down ladder operator is lowering us from n to
n 1.
One sees immediately that there is a lower bound to
the ladder, i.e., that one can not ladder down from the
lowest state, implying
M

|lowest >= 0 (4.4)

B. Form of the UpLadder Operator
What must the form of M
+
be, in order that it function
properly? Since
sin
_
(n + 1)x
L
_
= cos
_
x
L
_
sin
nx
L
+cos
_
nx
L
_
sin
_
x
L
_
One has, dening the up-ladder operator M
+
M
+
_
sin
_
nx
L
__
sin
_
(n + 1)x
L
_
= cos
__
x
L
__
sin
nx
L
+sin
_
x
L
_
cos
nx
L
which looks like
M
+
|n >cos
_
x
L
_
|n > +
_
L
n
_
sin
_
x
L
_
|n >
x
= |n+1 >
The
L
n
takes out the constant generated by the partial
derivative.
What this is saying is that there is an operator, M
+
,
which has a special form involving a multipier function
and a partial derivative, whose total eect on an eigen-
function is to ladder it from n to n + 1.
M
+
= cos
_
x
L
_
+
_
L
n
_
sin
_
x
L
_

x
written as an operator.
C. The DownLadder Operator
We need the down operator also, i.e.,
sin
_
(n 1)x
L
_
= cos
_
x
L
_
sin
nx
L
sin
_
x
L
_
cos
nx
L
making use of the even and odd properties of cosines and
sines, respectively.
M

|n >cos
_
x
L
_
|n >
_
L
n
_
sin
_
x
L
_
|n >
x
|n 1 >
M

= cos
_
x
L
_

_
L
n
_
sin
_
x
L
_

x
D. Ladder Operators in the Operator
Representation
Stated another way, in the traditional position-
momentum language, one has
M
+
= cos
x
L

_
L
n
_
sin
x
L
p
x
h
(4.5)
M

= cos
x
L
+
_
L
n
_
sin
x
L
p
x
h
(4.6)
5
E. Ladder Operators and the Hamiltonian
We need to show that this ladder operator works prop-
erly with the Hamiltonian, i.e.,
p
2
x
2m
H
op
(4.7)
and to do this we assume
H
op
|n >= |n >
and ask what happens when we operate from the left with
M
+
(for example). We obtain
M
+
H
op
|n >= M
+
|n > (4.8)
where we want to exchange the order on the l.h.s. so
that we can ascertain what the eigenvalue of the oper-
ator M
+
|n > i,, i.e., we need the commutator of the
Hamiltonian with the ladder operator,
[H
op
, M
+
] H
op
M
+
M
+
H
op
Remembering that
[p
x
, x] = h
one forms
[H
op
, M
+
] =
_
p
2
x
2m
__
cos
x
L
+
_
L
n
_
sin
x
L

x
_

_
cos
x
L
+
_
L
n
_
sin
x
L

x
__
p
2
x
2m
_
(4.9)
F. Some Precursor Commutators
First, one needs [p
x
, cos
x
L
],
[p
x
, cos
x
L
] h

x
cos
_
x
L
_
cos
_
x
L
_
_
h

x
_
(4.10)
which works out to be
[p
x
, cos
x
L
] = h

L
sin
_
x
L
_
= p
x
cos
x
L
cos
x
L
p
x
(4.11)
or, in the most useful form for future work:
p
x
cos
_
x
L
_
= cos
_
x
L
_
p
x
+h

L
sin
_
x
L
_
(4.12)
One needs the same commutator involving the appro-
priate sine also:
[p
x
, sin
_
x
L
_
] = h

L
cos
_
x
L
_
= p
x
sin
_
x
L
_
sin
_
x
L
_
p
x
(4.13)
p
x
sin
_
x
L
_
= sin
_
x
L
_
p
x
h

L
cos
_
x
L
_
(4.14)
Next, one needs [p
2
x
, cos
_
x
L
_
] (and its sine equivalent).
[p
2
x
, cos
_
x
L
_
] = p
2
x
cos
_
x
L
_
cos
_
x
L
_
p
2
x
(4.15)
= p
x
p
x
cos
_
x
L
_
cos
_
x
L
_
p
2
x
which we re-write, factoring, as
= p
x
_
cos
_
x
L
_
p
x
+h

L
sin
_
x
L
__
cos
_
x
L
_
p
2
x
which we re-write as
= p
x
cos
_
x
L
_
p
x
+h

L
_
p
x
sin
_
x
L
__
cos
_
x
L
_
p
2
x
=
_
h

L
sin
_
x
L
_
+ cos
_
x
L
_
p
x
_
p
x
+h

L
_
p
x
sin
_
x
L
__
cos
_
x
L
_
p
2
x
i.e.,
= h

L
sin
_
x
L
_
p
x
+ cos
_
x
L
_
p
2
x
+h

L
_
sin
_
x
L
_
p
x
h

L
cos
_
x
L
__
cos
_
x
L
_
p
2
x
= h

L
sin
_
x
L
_
p
x
+h

L
_
sin
_
x
L
_
p
x
h

L
cos
_
x
L
__
6
[p
2
x
, cos
_
x
L
_
] = 2h

L
sin
_
x
L
_
p
x
+ h
2
_

L
_
2
cos
_
x
L
_
p
2
x
cos
_
x
L
_
= 2h

L
sin
_
x
L
_
p
x
+ h
2
_

L
_
2
cos
_
x
L
_
+ cos
_
x
L
_
p
2
x
Now one needs [p
2
x
, sin
_
x
L
_
]
[p
2
x
, sin
_
x
L
_
] = p
2
x
sin
_
x
L
_
sin
_
x
L
_
p
2
x
(4.16)
= p
x
_
p
x
sin
_
x
L
__
sin
_
x
L
_
p
2
x
= p
x
_
sin
_
x
L
_
p
x
h

L
cos
_
x
L
__
sin
_
x
L
_
p
2
x
which we re-write as
=
_
p
x
sin
_
x
L
__
p
x
h

L
_
p
x
cos
_
x
L
__
sin
_
x
L
_
p
2
x
=
_
sin
_
x
L
_
p
x
h

L
cos
_
x
L
__
p
x
h

L
_
p
x
cos
_
x
L
__
sin
_
x
L
_
p
2
x
= h

L
_
cos
_
x
L
_
p
x
_

_
h

L
p
x
cos
_
x
L
__
i.e.,
= h

L
_
cos
_
x
L
_
p
x
_

_
h
_

L
__
cos
x
L
p
x
+h

L
sin
_
x
L
___
[p
2
x
, sin
_
x
L
_
] = 2h

L
cos
_
x
L
_
p
x
+ h
2
_

L
_
2
sin
_
x
L
_
p
2
x
sin
_
x
L
_
= 2h

L
cos
_
x
L
_
p
x
+ h
2
_

L
_
2
sin
_
x
L
_
+ sin
_
x
L
_
p
2
x
We had, in Equation 4.8 the following,
M
+
H
op
|n >= M
+
|n >
which we now wish to reverse. We need the commutator
of the Hamiltonian with the UpLadder Operator [3].
[H
op
, M
+
] =
p
2
x
2m
_
cos
_
x
L
_

L
n
_
sin
_
x
L
__
p
x
h
_
M
+
H
o
p
which becomes
[H
op
, M
+
] =
p
2
x
2m
cos
_
x
L
_

p
2
x
2m
L
n
_
sin
_
x
L
__
p
x
h
M
+
H
o
p (4.17)
expanding,
[H
op
, M
+
] =
1
2m
p
2
x
cos
_
x
L
_

1
2m
L
n
_
p
2
x
sin
_
x
L
__
p
x
h
M
+
H
o
p
and using the previously obtained commutators,
7
[H
op
, M
+
] =
1
2m
_
2h

L
sin
_
x
L
_
p
x
+ h
2
_

L
_
2
cos
_
x
L
_
+ cos
_
x
L
_
p
2
x
_

1
2m
L
n
_
2h

L
cos
_
x
L
_
p
x
h
2
_

L
_
2
sin
_
x
L
_
+ sin
_
x
L
_
p
2
x
_
p
x
h
M
+
H
o
p (4.18)
which expands, at rst, to
[H
op
, M
+
] =
1
2m
_
2h

L
sin
_
x
L
_
p
x
+ h
2
_

L
_
2
cos
_
x
L
_
_

1
2m
L
n
_
2h

L
cos
_
x
L
_
p
x
h
2
_

L
_
2
sin
_
x
L
_
_
p
x
h
(4.19)
[H
op
, M
+
] =
1
2m
_
2h

L
sin
_
x
L
_
p
x
+ h
2
_

L
_
2
cos
_
x
L
_
_
+
1
2m
1
n
_
2 cos
_
x
L
_
p
x

L
_
sin
_
x
L
_
_
p
x
(4.20)
2m[H
op
, M
+
] = 2h

L
sin
_
x
L
_
p
x
+ h
2
_

L
_
2
cos
_
x
L
_

2
n
cos
_
x
L
_
p
2
x

1
n
h

L
_
sin
_
x
L
_
p
x
(4.21)
2m[H
op
, M
+
] =
_
2h +
1
n
h

_

L
sin
_
x
L
_
p
x
+ h
2
_

L
_
2
cos
_
x
L
_
+
2
n
cos
_
x
L
_
p
2
x
(4.22)
2m[H
op
, M
+
] = h
_
2h +
1
n
h

_

L
_
sin
_
x
L
_
p
x
h
_
+ h
2
_

L
_
2
cos
_
x
L
_
+
2
n
cos
_
x
L
_
p
2
x
(4.23)
and substituting for
_
sin
_
x
L
_
px
h
_
one has
2m[H
op
, M
+
] = h
2
(1 + 2n)
_

L
_
2
_
M
+
cos
_
x
L
__
+ h
2
_

L
_
2
cos
_
x
L
_
+
2
n
cos
_
x
L
_
p
2
x
(4.24)
[H
op
, M
+
] = h
2
(1 + 2n)
2m
_

L
_
2
_
M
+
cos
_
x
L
__
+ h
2
1
2m
_

L
_
2
cos
_
x
L
_
+
2
n
cos
_
x
L
_
p
2
x
2m
(4.25)
[H
op
, M
+
] = h
2
(1 + 2n)
2m
_

L
_
2 _
M
+
_
h
2
(1 + 2n)
2m
_

L
_
2
_
cos
_
x
L
__
+ h
2
1
2m
_

L
_
2
cos
_
x
L
_
+
2
n
cos
_
x
L
_
p
2
x
2m
(4.26)
[H
op
, M
+
] = h
2
(1 + 2n)
2m
_

L
_
2 _
M
+
_
+
h
2
2m
_

L
_
2
(2n) cos
_
x
L
_
+
2
n
cos
_
x
L
_
H
op
(4.27)
1. Alternative Formulation

2
x
2
_
cos
_
x
L
_
+
L
n
sin
_
x
L
_

x
_
f =
8

x
_
cos
_
x
L
_

x


L
sin
_
x
L
_
+
L
n
sin
_
x
L
_

2
x
2
+
1
n
cos
_
x
L
_

x
_
f =

L
sin
_
x
L
_
f
x
+ cos
_
x
L
_

2
f
x
2

L
_
2
cos
_
x
L
_
f

L
sin
_
x
L
_
f
x
+
1
n
cos
_
x
L
_

2
f
x
2
+
L
n
sin
_
x
L
_

3
f
x
3

nL
sin
_
x
L
_
f
x
+
1
n
cos
_
x
L
_

2
f
x
2
(4.28)
So the commutator would be:

2
x
2
_
cos
_
x
L
_
+
L
n
sin
_
x
L
_

x
_
f
_
cos
_
x
L
_
+
L
n
sin
_
x
L
_

x
_

2
f
x
2
=

2
L
sin
_
x
L
_
f
x

L
_
2
cos
_
x
L
_
f
+
2
n
cos
_
x
L
_

2
f
x
2

nL
sin
_
x
L
_
f
x
(4.29)
or
=
_

2
L


nL
_
sin
_
x
L
_

x

_

L
_
2
cos
_
x
L
_
+
2
n
cos
_
x
L
_

2
x
2
(4.30)
=
_

2
L


nL
_
n
L
_
M
+
cos
_
x
L
__

L
_
2
cos
_
x
L
_
+
2
n
cos
_
x
L
_

2
x
2
(4.31)

2m
h
2
[H, M
+
] =
_

L
_
2
(2n 1)
_
M
+
cos
_
x
L
__

L
_
2
cos
_
x
L
_
+
2
n
cos
_
x
L
_

2
x
2
(4.32)

2m
h
2
[H, M
+
] =
_

L
_
2
(2n + 1) M
+
+
_

L
_
2
(2n) cos
_
x
L
_
+
2
n
cos
_
x
L
_

2
x
2
(4.33)
[H, M
+
] =
h
2
2m
_

L
_
2
(2n + 1) M
+
+
_

L
_
2
(2n) cos
_
x
L
_
+
2
n
cos
_
x
L
_

2
x
2
_
(4.34)
[H, M
+
] =
h
2
2m
_

L
_
2
(2n + 1) M
+
+ 2n
_

L
_
2
cos
_
x
L
_
_

2
n
cos
_
x
L
_
h
2
2m

2
x
2
(4.35)
H|n >=
n
|n >
and, operating from the left with M
+
one has
M
+
H|n >=
n
M
+
|n >=
n
|n + 1 >
9
and since [H, M
+
] = HM
+
M
+
H, one has
HM
+
|n > [H, M
+
]|n >=
n
|n + 1 >
H|n + 1 > [H, M
+
]|n >=
n
|n + 1 >
H|n + 1 > +
h
2
2m
_

L
_
2
(2n + 1) M
+
+ 2n
_

L
_
2
cos
_
x
L
_
_
|n > +
2
n
cos
_
x
L
_
h
2
2m

2
x
2
|n >=
n
|n + 1 >
H|n + 1 > +
h
2
2m
_

L
_
2
(2n + 1) M
+
+ 2n
_

L
_
2
cos
_
x
L
_
_
|n >
2
n
cos
_
x
L
_

n
|n >=
n
|n + 1 >
H|n + 1 > +
h
2
2m
_

L
_
2
(2n + 1)M
+
+
_
2n
_

L
_
2

4m
nh
2

n
_
cos
_
x
L
_
_
|n >=
n
|n + 1 >
H|n + 1 > +
h
2
2m
_

L
_
2
(2n + 1)M
+
_
|n > +
_
2n
_

L
_
2

4m
nh
2

n
_
cos
_
x
L
_
|n >=
n
|n + 1 >
H|n + 1 > +
h
2
2m
_

L
_
2
(2n + 1)
_
|n + 1 > +
_
2n
_

L
_
2

4m
nh
2

n
_
cos
_
x
L
_
|n >=
n
|n + 1 >
H|n + 1 > +
_
2n
_

L
_
2

4m
nh
2

n
_
cos
_
x
L
_
|n >=
n
|n + 1 > +
h
2
2m
_
_

L
_
2
(2n + 1)
_
|n + 1 >
From this we conclude that, if the elements in square
brackets cancelled perfectly, M
+
|n + 1 > would be an
eigenfunction, i.e., if
+
_
2n
_

L
_
2

4m
nh
2

n
_
= 0 (4.36)
i.e.,

n
=
n
2
h
2

2
2m L
2
then
H|n + 1 >=
_

n
+
h
2
2m
_
_

L
_
2
(2n + 1)
__
|n + 1 >
Sines and cosines form a complete orthonormal set, suit-
able for Fourier Series expansion, where ortho means
that each member is orthogonal to every other member,
and normal means that one can normalize them (if one
wishes). There are other such sets, and each of them
shows up in standard Quantum Chemistry, so each needs
to be addressed separately.
V. HERMITE POLYNOMIALS
The relevant Schrodinger Equation is

h
2
2

2
z
2
+
k
2
z
2
= E (5.1)
where k is the force constant (dynes/cm) and is the
reduced mass (grams). Cross multiplying, one has

2
z
2

k
h
2
z
2
=
2
h
2
E (5.2)
which would be simplied if the constants could be sup-
pressed. To do this we change variable, from z to some-
thing else, say x, where z = x. Then

z
=
x
z

x
=
1

x
so
_
1

2
_

2
x
2

k
h
2

2
x
2
=
2
h
2
E (5.3)
and

2
x
2

k
h
2

4
x
2
=
2
2
h
2
E (5.4)
10
which demands that we treat
1 =
k
h
2

4
=
_
1
k
h
2
_
1/4
=
_
h
2
k
_1/4
With this choice, the dierential equation becomes

x
2
x
2
= (5.5)
where
=
2
2
E
h
2
=
2
_
h
2
k
E
h
2
=
2E
_

k
h
A. A Guessed Solution
The easiest solution to this dierential equation is
e

x
2
2
which leads to = 1 and
E =
h
2

B. Laddering up on the Guessed Solution

Given

0
= |0 >= e

x
2
2
with = 1, it is possible to generate the next solution by
using
N
+
=

x
+x (5.6)
as an operator, which ladders up from the ground (n=0)
state to the next one (n=1) To see this we apply N
+
to

0
obtaining
N
+

0
= N
+
|0 >=
_

x
+x
_
e

x
2
2
= (x)
0
+x
0
= 2xe
x
2
/2
=
1
= |1 > (5.7)
Doing this operation again, one has
N
+

1
= N
+
|1 >=
_

x
+x
_
2xe

x
2
2
= (2+4x
2
)e
x
2
/2
(5.8)
etc., etc., etc..
C. Generating Hermites dierential equation
Assuming
= e
x
2
/2
H(x)
where H(x) is going to become a Hermite polynomial.
One then has
d
dx
= xe
x
2
/2
H(x) +e
x
2
/2
dH(x)
dx
and
d
2

dx
2
= e
x
2
/2
H(x) +x
2
e
x
2
/2
H(x) 2xe
x
2
/2
dH(x)
dx
+e
x
2
/2
d
2
H(x)
dx
2
From Equation 5.5 one has,

2
x
2
x
2
= e
x
2
/2
H(x) 2xe
x
2
/2
dH(x)
dx
+e
x
2
/2
d
2
H(x)
dx
2
= e
x
2
/2
H(x) (5.9)
or
H(x) 2x
dH(x)
dx
+
d
2
H(x)
dx
2
= H(x) (5.10)
which we re-write in normal lexicographical order
d
2
H(x)
dx
2
2x
dH(x)
dx
(1 )H(x) = 0 (5.11)
11
D. An alternative solution scheme
Starting with
dy
dx
+ 2xy = 0 (5.12)
one has
dy
y
= 2xdx
so, integrating each side separately, one has
ny = x
2
+nC
or, inverting the logarithm,
y = Ce
x
2
We now dierentiate Equation 5.12, obtaining
d
2
y
dx
2
+ 2
d(xy)
dx
=
d
2
y
dx
2
+ 2x
dy
dx
+ 2y
dx
dx
=
d
2
y
dx
2
+ 2x
dy
dx
+ 2y = 0 ; n = 0 (5.13)
Doing this again, i.e., dierentiating this (second) equation (Equation 5.13), one has
d
d
2
y
dx
2
dx
+
d2x
d(y)
dx
dx
+ 2
dy
dx
=
d
2
_
dy
dx
_
dx
2
+ 2x
d
_
dy
dx
_
dx
+ 4
_
dy
dx
_
= 0 ; n = 1
which is the same equation, (but with a 4 multiplier of
the last term) applied to the rst derivative of y. Take
the derivative again:
d
_
d
2 dy
dx
dx
2
+ 2x
d
dy
dx
dx
+ 4
dy
dx
_
dx
= 0
i.e.,
d
2
_
d
2
y
dx
2
_
dx
2
+ 2x
d
_
d
2
y
dx
2
_
dx
+ 6
_
d
2
y
dx
2
_
= 0
d
2
f(x)
dx
2
+ 2x
df(x)
dx
+ 6f(x) = 0 ; n = 2
f(x) has the form g(x)e
x
2
where g(x) is a polynomial
in x.
d
2
g(x)e
x
2
dx
2
+ 2x
dg(x)e
x
2
dx
+ 2(n + 1)g(x)e
x
2
= 0
i.e.,
_
g

(x) 4xg

(x) 2g(x) + 4x
2
g(x) + 2xg

(x) 4x
2
g(x) + 2(n + 1)g(x)
_
e
x
2
= 0
or
g

(x) 2xg

(x) + 2ng(x) = 0
and we had (see Equation 5.11)
H

(x) 2xH

(x) (1 )H(x) = 0
which leads to
2n = 1 +
i.e.,
= 1 + 2n =
2E
_
/k
h
i.e.,
E = h(n + 1/2)

E. Frobenius Method
The most straight forward technique for handling the
Hermite dierential equation is the method of Frobenius.
We assume a power series Ansatz (ignoring the indicial
equation argument here), i.e.,
=

i=0
a
i
x
i
12
and substitute this into Equation 5.11, obtaining

x
2
=

i=2
i(i 1)a
i
x
i2
2x

x
= 2

i=1
ia
i
x
i
( 1) = ( 1)

i
a
i
x
i
= 0
i.e.,

x
2
= 2(1)a
2
+ (3)(2)a
3
x + (4)(3)a
4
x
2
+
2x

x
= 2a
1
x
1
2a
2
x
2
2a
3
x
3

( 1) = ( 1)a
0
+ ( 1)a
1
x + ( 1)a
2
x
2
= 0
which leads to
(3)(2)a
3
+ ( 1)a
1
2a
1
= 0 (odd)
(4)(3)a
4
2a
2
+ ( 1)a
2
= 0 (even)
(5)(4)a
5
2a
3
+ ( 1)a
3
= 0 (odd)
etc., which shows a clear distinction between the even
and the odd powers of x. We can solve these equations
sequentially.
We obtain
a
3
=
2 + 1
(3)(2)
a
1
a
4
=
2 + 1
(4)(3)
a
2
=
_
2 + 1
(4)(3)
__
1
(2)(1)
_
i.e.,
a
4
=
_
(3 )(1 )
(4)(3)(2)(1)
_
etc..
This set of even (or odd) coecients leads to a series
which itself converges unto a function which grows to
positive innity as x varies, leading one to require that
the series be terminated, becoming a polynomial.
We leave the rest to you and your textbook.
VI. LEGENDRE POLYNOMIALS
A. From Laplaces Equation
There are so many dierent ways to introduce Leg-
endre Polynomials that one searchs for a path into this
subject most suitable for chemists.
Consider Laplaces Equation:

2
=

2

x
2
+

2

y
2
+

2

z
2
= 0 (6.1)
which is a partial dierential equation for (x, y, z). For
our purposes, the solutions can be obtained by guessing,
starting with = 1, and proceeding to = x, = y and
= z. It takes only a little more imagination to obtain
= xy and its associates = yz and = xz. It takes
just a little more imagination to guess = x
2
y
2
, but
once done, one immediately guesses its two companions
= x
2
z
2
and = y
2
z
2
.
Reviewing, there was one simple (order 0) solution,
three not so simple, but not particularly dicult solu-
tions (of order 1) and six slightly more complicated solu-
tions of order 2. Note that the rst third-order solution
one might guess would be = xyz!
If one looks at these solutions, knowing that they are
quantum mechanically important, the 1, x, y, and z so-
lutions, accompanied by the xy, xz, yz, and x
2
y
2
so-
lutions suggest something having to do with wave func-
tions, where the rst function (1) is associated in some
way with s-orbitals, the next three (x, y, and z) are as-
sociated with p-orbitals, and the next (of order 2) are
associated with d-orbitals. If all this is true, the per-
ceptive student will wonder where is the d
z
2 orbital, the
fth one, and how come there are six functions of order
two listed, when, if memory serves correctly, there are 5
d-orbitals! Ah.
_
y
2
z
2
_
+
_
x
2
y
2
_
can be rewritten as
_
y
2
z
2
_
+
_
x
2
y
2
_
+
_
z
2
z
2
_
which is
x
2
+y
2
+z
2
3z
2
or as
r
2
3z
2
which combines the last two (linearly dependent) solu-
tions into one, the one of choice, which has been employed
for more than 50 years as the d
z
2 orbital.
In Spherical Polar Coordinates, these solutions become
13
1 1
x r sin cos
y r sin sin
z r cos
xy r sin cos r sin sin = r
2
sin
2
cos sin
xz r sin cos r cos = r
2
sin cos cos
yz r sin sin r cos = r
2
sin cos sin
x
2
y
2
r
2
sin
2
cos
2
r
2
sin
2
sin
2
= r
2
_
sin
2

_
cos
2
sin
2

_
r
2
3z
2
r
2
3r
2
cos
2
= r
2
_
1 3 cos
2

_
.
.
. (6.2)
Now, Laplaces equation in spherical polar coordinates
is

2
=
1
r
2
r
2
r
r
+
1
r
2
sin
2

_
sin
sin

+

2

2
_
= 0
(6.3)
Next, we notice that our earlier solutions were all of the
form
= r

Y
,m

(r, , ) (6.4)
where species the order, 0, 1, 2, etc., and the func-
tion of angles is dependent on this order, and on another
quantum number as yet unspecied. Substituting this
form into the spherical polar form of Laplaces equation
results in a new equation for the angular parts alone,
which we know from our previous results. We substitute
Equation 6.4 into Equation 6.3 to see what happens, ob-
taining

2
r

Y
,m

=
1
r
2
r
2
r

Y
,m

r
r
+
1
r
2
sin
2

_
_
sin
sin
r

Y
,m

+

2
r

Y
,m

2
_
_
= 0
which, by the nature of partial dierentiation, becomes

2
r

Y
,m

= Y
,m

1
r
2
r
2 r

r
r
+r

1
r
2
sin
2

_
sin
sin
Y
,m

+

2
Y
,m

2
_
= 0 (6.5)
and the rst term in Equation 6.5 is
1
r
2
r
2 r

r
r
=
1
r
2
( + 1)r

(6.6)
so, substituting into Equation 6.5 we obtain

2
r

Y
,m

= ( + 1)r
2
Y
,m

+r
2
1
sin
2

_
sin
sin
Y
,m

+

2
Y
,m

2
_
= 0 (6.7)
which, of course, upon cancelling common terms, gives
(+1)Y
,m

+
1
sin
2

_
sin
sin
Y
,m

+

2
Y
,m

2
_
= 0
(6.8)
Laplaces Equation in Spherical Polar Coordinates on the
unit sphere, i.e. Legendres Equation!
14
What then are these angular solutions we found?
= 0; 1
= 1; sin cos
= 1; sin sin
= 1; cos
= 2; sin
2
cos sin
= 2; sin cos cos
= 2; sin cos sin
= 2;
_
sin
2

_
cos
2
sin
2

_
= 2;
_
1 3 cos
2

_
.
.
. (6.9)
and if you check back concerning their origin, you will
see where the Hydrogenic Orbitals naming pattern comes
from for s, p and d orbitals.
These functions have been written in real form, and
they have complex (not complicated) forms which al-
low a dierent simplication:
1s = 0; 1
2p
x
= 1; sin
e

+e

2
2p
y
= 1; sin
_
e

2
_
2p
z
= 1; cos
3d
xy
= 2; sin
2

_
e

+e

2
__
e

2
_
3d
xz
= 2; sin cos
e

+e

2
3d
yz
= 2; sin cos
_
e

2
_
3d
x
2
y
2 = 2;
_
sin
2

_
_
e

+e

2
_
2

_
e

2
_
2
__
3d
z
2 = 2;
_
1 3 cos
2

_
.
.
. (6.10)
Once they have been written in imaginary form, we can
create intelligent linear combinations of them which illu-
minate their underlying structure. Consider 2p
x
+ 2p
y
which becomes
sin e

(employing DeMoivres theorem) aside from irrelevant

constants. Next consider 2p
x
2p
y
which becomes
sin e

We have a trio of functions

2p
m

=1
= sin e

2p
m

=0
= cos
2p
m

=+1
= sin e
+
(6.11)
(6.12)
which correspond to the m

values expected of p-orbitals.

You will see that the same trick can be applied to
d
xz
and d
yz
.
Finally, the same trick, almost, can be applied to d
xy
and d
x
2
y
2 with the m

= 0 value reserved for d

z
2, all by
itself.
15
B. From the Hydrogen Atom
Perhaps the next best place to introduce Spherical Har-
monics and Legendre Polynomials is the Hydrogen Atom,
since its eigenfunctions have angular components which
are known to be Legendre Polynomials.
The Schrodinger Equation for the H-atom is

h
2
2m
e

2
|n, , m

>
Ze
2
r
|n, , m

>= E
n
|n, , m

>
(6.13)
We know that this equation is variable separable, in
the sense that
|n, , m

>= R
n,
(r)Y
,m

(, )
Here, R
n,
is the radial wave function, and Y
,m

is the
angular wave function (a function of two variables), Since

2
=
1
r
2

r
2

r
r
+
1
r
2
sin
2

_
sin
sin

+

2

2
_

2
|n, , m

>=
2
R
n,
(r)Y
,m

(, ) =
Y
r
2
r
2 R
r
r
+
R
r
2
sin
2

_
sin
sin
Y

+

2
Y

2
_
which means that the Schrodinger Equation has the form

h
2
2m
e
_
Y
r
2
r
2 R
r
r
+
R
r
2
sin
2

_
sin
sin
Y

+

2
Y

2
__

Ze
2
r
RY = E
n
RY
Dividing through by R
n,
Y
,m

(abreviated as RY) we have

h
2
2m
e
_
1
Rr
2
r
2 R
r
r
+
1
r
2
Y sin
2

_
sin
sin
Y

+

2
Y

2
__

Ze
2
r
= E
n
Multiplying through by r
2
shows that the expected variable separation has resulted in a proper segregation of the
angles from the radius.
1
R
r
2 R
r
r
+
1
Y sin
2

_
sin
sin
Y

+

2
Y

2
_
. .
+
2mZe
2
r
h
2
=
2m
h
2
E
n
r
2
We can see this by noting that the underbracketed part
of this last equation is a pure function of angles, with no
radius explicitly evident.
It is now standard to obtain (recover?) the equation
(6.8)
1
Y sin
2

_
sin
sin
Y

+

2
Y

2
_
= ( + 1) (6.14)
where the minus sign (which is essentially arbitrary) is
demanded by convention.
Cross multipilying by Y, one has
1
sin
2

_
sin
sin
Y

+

2
Y

2
_
= ( + 1)Y (6.15)
which is written in traditional eigenfunction/eigenvalue
form.
C. Another Form for the Legendre Dierential
Equation
A change of variables can throw this equation (Equa-
tion 6.15) into a special form, which is sometimes illumi-
nating. We write
= cos
and

= sin =
_
1 cos
2
=
_
1
2
so

=
_

which is, substituting into Equation 6.15

=
_

_
1
2
_

16
1
(1
2
)
_
_
1
2
_
1
2

_
1
2
_
1
2
Y

+

2
Y

2
_
= ( + 1)Y (6.16)
where the (+1) form is a dierent version of a constant,
looking ahead to future results!
_
_

_
(1
2
)
Y

+

2
Y

2
_
_
= ( + 1)Y (6.17)
where
Y
,m

(, ) = e
m

S
,m

()
For m

= 0 we have
_
_

_
(1
2
)
S
,0

_
_
= ( + 1)S
,0
(6.18)
i.e., Legendres equation.
D. Schmidt Orthogonalization
We assume polynomials in
n
and seek orthonormal
combinations which can be generated starting with a con-
stant (n=0) term. Then the normalization integral
< 0|0 >=
_
1
+1

2
0
d = 1
[4] implies that
|0 >=
_
1
2
We now seek a function |1 > orthogonal to |0 > which
itself is normalizeable. We have
0 =< 1|0 >=
_
1
+1

1
_
1
2
d
which has solution
1
= N
1
x. Normalizing, we have
< 1|1 >=
_
1
+1

2
1
d = 1 =
_
1
+1
N
2
1

2
d
which yields
1 = N
2
1
2
3
i.e.,
|1 >=
_
3
2
x
To proceed, we need to generate a function |2 > which
is not only normalizeable but orthogonal to |0 > and
|1 >.
< 2|0 >=
_
1
+1

2
_
1
2
d = 0
and
< 2|1 >=
_
1
+1

2
_
2
3
d = 0
where |2 > is a polynomial of order 2 in , i.e.,

2
= |2 >= a
2
+b
Substituting, we have
< 2|0 >=
_
1
+1
(a
2
+b)
_
1
2
d = 0
and
< 2|1 >=
_
1
+1
(a
2
+b)
_
3
2
d = 0
We obtain two equations in two unknowns, a and b,
_
1
2
_
2a
3
+ 2b
_
= 0
and the other integral vanishes automatically. i.e.,
a
3
+b = 0
i.e., a = 3b so
|2 >= 3b
2
+b
in unnormalized form. Normalizing gives
< 2|2 >=
_
1
+1
(3b
2
+b)
2
d = 1
i.e.,
< 2|2 >= b
2
_
1
+1
(3
2
+ 1)
2
d = 1
which gives
b =

1
_
1
+1
(3
2
+ 1)
2
d
where, of course, we recognize the sign ambiguity in this
result.
One can continue forever with this Schmidt Orthog-
onalization, but the idea is clear, and there are better
ways, so why continue?
17
E. Frobenius Solution to Legendres Equation
We start a Frobenius solution without worrying about
the technical details of the indicial equation, and just
assert that the proposed solution Ansatz will be
S
,0
() = y() =

n=0
c
n

n
= c
0
+c
1
+c
2

2
+ (6.19)
which we substitute into the dierential equation:

_
(1
2
)
y()

= ( + 1)y() (6.20)
which leads to

_
y()

2
y()

+( + 1)y() = 0 (6.21)

2
y()

2

2

2
y()

2
2
y()

+(+1)y() = 0 (6.22)
so that when we feed the Ansatz into this dierential
equation we obtain
(2)(1)c
2
+ (3)(2)c
3
+ (4)(3)c
4

2
+ (5)(4)c
5

2
_
(2)(1)c
2
+ (3)(2)c
3
+ (4)(3)c
4

2
+ (5)(4)c
5

3

_
2
_
c
1
+ (2)c
2
+ (3)c
3

2
+ (4)c
4

3
+
_
+( + 1)
_
c
0
+c
1
+c
2

2
+c
3

3
+
_
= 0 (6.23)
(2)(1)c
2
+ (3)(2)c
3
+ (4)(3)c
4

2
+ (5)(4)c
5

3

(2)(1)c
2

2
(3)(2)c
3

3
(4)(3)c
4

4
(5)(4)c
5

5

2c
1
2(2)c
2

2
2(3)c
3

3
2(4)c
4

4

+( + 1)c
0
+( + 1)c
1
+( + 1)c
2

2
+( + 1)c
3

3
+ = 0 (6.24)
which, in standard Frobenius form, we separately equate
to zero (power by power) to achieve the appropriate re-
cursion relationships. Note that there is an even and an
odd set, based on starting the c
0
or c
1
, which correspond
to the two arbitrary constants associated with a second
order dierential equation. We obtain
(2)(1)c
2
+( + 1)c
0
= 0
+(3)(2)c
3
2c
1
+( + 1)c
1
= 0
+(4)(3)c
4

2
(2)(1)c
2

2
2(2)c
2

2
+( + 1)c
2

2
= 0
(5)(4)c
5

3
(3)(2)c
3

3
2(3)c
3

3
+( + 1)c
3

3
= 0
(4)(3)c
4

4
2(4)c
4

5
+ etc = 0
(2)(1)c
2
+( + 1)c
0
= 0
+(3)(2)c
3
2c
1
+( + 1)c
1
= 0
+(4)(3)c
4
(2)(1)c
2
2(2)c
2
+( + 1)c
2
= 0
(5)(4)c
5
(3)(2)c
3
2(3)c
3
+( + 1)c
3
= 0
(4)(3)c
4

4
2(4)c
4

5
etc + = 0 (6.25)
(2)(1)c
2
= ( + 1)c
0
+(3)(2)c
3
= (2 ( + 1))c
1
+(4)(3)c
4
= ((2)(1) + 2(2) ( + 1))c
2
(5)(4)c
5
((3)(2) + 2(3) ( + 1))c
3
(4)(3)c
4

4
2(4)c
4

5
etc + = 0 (6.26)
c
2
=
( + 1)
2!
c
0
c
3
=
(2 + ( + 1))
(3)(2)
c
1
c
4
=
((2)(1) 2(2) +( + 1))
(4)(3)
c
2
c
5
=
((3)(2) 2(3) +( + 1))
(5)(4)
c
3
etc. (6.27)
which we re-write in terms of c
0
and c
1
only, i.e.,
c
2
=
( + 1)
2!
c
0
c
3
=
(2 +( + 1))
(3)(2)
c
1
+
c
4
=
_
((2)(1) 2(2) +( + 1))
(4)(3)
__
(
( + 1)
2!
_
c
0
c
5
=
_
((3)(2) 2(3) +( + 1))
(5)(4)
__

(2 +( + 1))
(3)(2)
_
c
1
etc. (6.28)
so S
,0
() = f
1
c
0
+f
2
c
1
where f
1
and f
2
are power series
based on the above set of coecients. For an even series,
declare c
1
= 0 and choose an value which truncates the
18
power series into a polynomial. Do the opposite for an
odd solution.
F. Rodriques Formula
Rodriques formula is
S
,0
P

() =
1
2

!
d

(
2
1)

where Legendres Equation is

(1
2
)
P

()
d
2
2
dP

d
+( + 1)P

() = 0
To show this, we start by dening
g

(
2
1)

and nd that
dg

d
= 2(
2
1)
1
and
d
2
g

d
2
= 2(
2
1)
1
+ 4
2
( 1)(
2
1)
2
We now form (construct)
(1
2
)
d
2
g

d
2
= 2(
2
1)

4
2
( 1)(
2
1)
1
2( 1)
dg

d
= 4
2
( 1)(
2
1)
1
+2g

= 2(
2
1)

(6.29)
The r.h.s. of this equation set adds up to zero, and one obtains on the left:
A() = (1
2
)
d
2
g

d
2
+ 2( 1)
dg

d
+ 2g

= 0 (6.30)
Dening the l.h.s of this equation as A(), we form
dA()
d
=
_
(1
2
)
d
3
d
3
2
d
2
d
2
+ 2( 1)
d
2
d
2
+ 2( 1)
d
d
+ 2
d
d
_
g

=
_
(1
2
)
d
2
d
2
(2 4)
d
d
+ (4 2)
_
dg

d
d
2
A()
d
2
=
_
(1
2
)
d
2
d
2
(2 6)
d
d
+ (6 6)
_
d
2
g

d
2
d
3
A()
d
3
=
_
(1
2
)
d
2
d
2
(2 8)
d
d
+ (8 12)
_
d
3
g

d
3
Continuing, one notices that the changing coecients are
regular in their appearance, so that the following table,
which summarizes the pattern of coecients,
= 1 2 4 = 2 2 ( + 1) 4 2 = (3 +) 2 =6 if = 1
= 2 2 6 = 2 2 ( + 1) 6 6 = (3 +) 2 = 6 if = 2
= 3 2 8 = 2 2 ( + 1) 8 12 = (3 +) 2 = 12 if = 3
.
.
.
.
.
.
.
.
.
.
.
.
= 2 2 ( + 1) = 2 8 12 = (3 +) 2 = ( + 1)
leads to generalization by which one nally obtains

A(x)

=
_
(1
2
)

2

2
2

+( + 1)
_
g

()
d

(6.31)
so, if
d

KP

()
19
with K constant, then
P

() =
1
K
d

=
1
K
d

(
2
1)

Here,
2

!
is chosen for Ks value to make the normalization auto-
matic.
G. Generating Function for Legendre Polynomials
The technically correct generating function for Legen-
dre polynomials is via the equation
1

1 2xu +u
2
=

0
P
n
(x)u
n
(6.32)
Here, we expand the denominator using the binomial the-
orem,
1
(1 +y)
m
= 1my+
m(m+ 1)
2!
y
2

m(m+ 1)(m+ 2)
3!
y
3
+
where m =
1
2
and the series converges when y < 1. Notice
that it is an alternating series. Identifying y = u
2
2xu
we have
1
(1 2xu +u
2
)
(
1/2)
= 1(1/2)(u
2
2xu)+
(1/2)((1/2) + 1)
2!
(u
2
2xu)
2

(1/2)((1/2) + 1)((1/2) + 2)
3!
(u
2
2xu)
3
+
which we now re-arrange in powers of u (in the mode required by Equation 6.32), obtaining
1
(1 2xu +u
2
)
1/2
= 1
u
2
2
+xu +
(3/4)
2!
(u
4
4xu
3
+ 4x
2
u
2
)
(1/2)(3/2)(5/2)
3!
(u
2
2xu)
3
+
1. Alternative Generating Function Method
Another method of introducing Legendre Polynomials
is through the generating function. Since this method
is very important in Quantum Mechanical computations
concerning poly-electronic atoms and molecules, it is
worth our attention. When one considers the Hamilto-
nian of the Helium Atoms electrons, one has

Ze
2
r
1

Ze
2
r
2
+
e
2
r
12
(6.33)
where r
12
is the distance between electron 1 and elec-
tron 2, i.e., it is the electron-electron repulsion term. We
examine this term in this discussion. We can write this
electron-electron repulsion term as
1
r
12
=
1
_
r
2
1
+r
2
2
2r
1
r
2
cos
(6.34)
where r
1
and r
2
are the distances from the nucleus to
electrons 1 and 2 respectively. is the angle between
the vectors from the nucleus to electron 1 and electron
2. It is required that we do this is two domains, one in
which r
1
> r
2
and one in which r
2
> r
1
. This is done for
convergence reasons (vide infra). For the rst case, we
dene
=
r
2
r
1
so that < 1, and Equation 6.34 becomes
1
r
12
=
1
r
1
1
_
1 +
2
2 cos
(6.35)
which we now expand in a power series in cos (which
will converge while zeta < 1). We have
1
r
1
1
_
1 +
2
2 cos
=
1
r
1
_
_
_
_
1 +
1
1!
d
_
1

1+
2
2 cos
_
d cos

cos =0
cos +
1
2!
d
2
_
1

1+
2
2 cos
_
d cos
2

cos =0
cos
2
+
_
_
_
_
(6.36)
20
It is customary to change notation from cos to , so
1
r
12
=
1
r
1
1
_
1 +
2
2
(6.37)
which we now expand in a power series in (which will
converge while < 1). We have
1
r
1
1
_
1 +
2
2
=
1
r
1
_
_
_
_
1 +
1
1!
d
_
1

1+
2
2
_
d

=0
+
1
2!
d
2
_
1

1+
2
2
_
d
2

=0

2
+
_
_
_
_
+ (6.38)
which we leave in this form, ready to evaluate and equate
to earlier versions of this expansion.
H. The Expansion of a Finite Dipole in Legendre
Polynomials
There is yet another way to see Legendre Polynomials
in action, through the expansion of the potential energy
of point dipoles. To start, we assume that we have a
dipole at the origin, with its positive charge (q) at (0,0,-
a/2) and its negative charge (q) at (0,0,+a/2), so that
the bond length is a, and therefore the dipole mo-
ment is qa.
At some point P(x, y, z), located (also) at r,,, we
have that the potential energy due to these two point
charges is
U(x, y, z, a) =
q
_
x
2
+y
2
+ (z a/2)
2
+
q
_
x
2
+y
2
+ (z +a/2)
2
which is just Coulombs law.
If we expand this potential energy as a function of a,
the bond distance, we have
U(x, y, z, a) = U(x, y, z, 0) +
1
1!
dU
da

a=0
a +
1
2!
d
2
U
da
2

a=0
a
2
+
1
3!
d
3
U
da
3

a=0
a
3
+
All we need do, now, is evaluate these derivatives. We have, for the rst
1
1!
dU
da

a=0
= q
_

_
1
2
_
2(z a/2)(1/2)
(x
2
+y
2
+ (z a/2)
2
))
3/2
_
+
_

_
1
2
_
2(z +a/2)(1/2)
(x
2
+y
2
+ (z +a/2)
2
))
3/2
__
which is, in the limit a 0,
q
_

z
r
3
_
so, we have, so far,
U(x, y, z, a) = 0 qa
_
z
r
3
_
+ = qa
_
cos
r
2
_
+
i.e., to the dipolar form.
For the second derivative, we take the derivative of the
rst derivative:
1
2!
d
dU
da
da

a=0
= q
1
2 2!
_
_
d
__
(za/2)
(x
2
+y
2
+(za/2)
2
))
3/2
_
+
_
(z+a/2)
(x
2
+y
2
+(z+a/2)
2
))
3/2
__
da
_
_
which equals zero. The next term gives
q
cos
_
3 5 cos
2

_
8r
4
a
3
and so it goes.
21
I. Alternative Formulations for Angular
Momentum Operators
To proceed, it is of value to inspect the angular mo-
mentum operator in terms of angles rather than Carte-
sian coordinates.
Remember that
x = r sin cos
y = r sin sin
z = r cos
We start with a feast of partial derivatives:
_
r
x
_
y,z
= sin cos (6.39)
_
r
y
_
x,z
= sin sin (6.40)
_
r
z
_
x,y
= cos (6.41)
_

x
_
y,z
=
cos cos
r
(6.42)
_

y
_
x,z
=
cos sin
r
(6.43)
_

z
_
x,y
=
sin
r
(6.44)
and nally
_

x
_
y,z
=
sin
r sin
(6.45)
_

y
_
x,z
=
cos
r sin
(6.46)
_

z
_
x,y
= 0 (6.47)
which we employ on the dened x-component of the an-
gular momentum, thus
L
x
yp
z
zp
y
= hsin sin

z

_
hcos

y
_
where

z
=
_
r
z
_
x,y

r
+
_

z
_
x,y

+
_

z
_
x,y

= (cos )

r
+
_
sin
r
_

+ (0)

and

y
=
_
r
y
_
x,z

r
+
_

y
_
x,z

+
_

y
_
x,z

= (sin sin )

r
+
_
cos sin
r
_

+
_
cos
r sin
_

and parenthetically,

x
=
_
r
x
_
y,z

r
+
_

x
_
y,z

+
_

x
_
y,z

= (sin cos )

r
+
_
cos cos
r
_

+
_

sin
r sin
_

so,
L
x
yp
z
zp
y
= hr sin sin
_
(cos )

r
+
_

sin
r
_

_
hr cos
_
(sin sin )

r
+
_
cos sin
r
_

+
_
cos
r sin
_

__
(6.48)
At constant r, the partial with respect to r looses mean- ing, and one has
L
x
h
= r sin sin
_
+
_

sin
r
_

_
cos
__
cos sin
r
_

+
_
cos
r sin
_

_
(6.49)
22
which leads to (combining the partial derivative terms
and cancelling the r terms)
L
x
= h
_
sin

+
cos cos
sin

_
(6.50)
and similar arguments lead to
L
y
= h
_
cos

cos sin
sin

_
(6.51)
L
z
= h

(6.52)
with
L
2
= h
2
_
1
sin
2

_
sin

+

2

2
__
(6.53)
We see that the operator associated with Legendres
Equation (multiplied by a constant) has emerged, mean-
ing that Legendre Polynomials and angular momentum
are intimately asssociated together.
J. Ladder Operator for Angular Momentum
Dening
L
+
= L
x
+L
y
and
L

= L
x
L
y
and knowing
L
x
L
y
L
y
L
z
= (yp
z
zp
y
)(zp
x
xp
z
)(zp
x
xp
z
)(yp
z
zp
y
)
which is
= yp
z
zp
x
yp
z
xp
z
zp
y
zp
x
+zp
y
xp
z
zp
x
yp
z
+zp
x
zp
y
+xp
z
yp
z
xp
z
zp
y
= yp
z
zp
x
which is, reordering:
= yp
z
zp
x
zp
x
yp
z
yp
z
xp
z
+xp
z
yp
z
zp
y
zp
x
+zp
x
zp
y
+zp
y
xp
z
xp
z
zp
y
which is, cancelling:
= yp
z
zp
x
zp
x
yp
z
+zp
y
xp
z
xp
z
zp
y
= yp
x
(p
z
z zp
z
) +xp
y
(zp
z
p
z
z)
= yp
x
(h) +xp
y
(h)
= h(xp
y
yp
x
) = hL
z
= [L
x
, L
y
]
that
[L
x
, L
y
] = hL
z
(6.54)
[L
y
, L
z
] = hL
x
(6.55)
[L
z
, L
x
] = hL
y
(6.56)
and knowing
[L
x
, L
+
] = L
x
(L
x
+L
y
) (L
x
+L
y
)L
x
which is, expanding:
= L
x
L
x
+L
x
L
y
L
x
L
x
L
y
L
x
= L
x
L
x
L
x
L
x
+(L
x
L
y
L
y
L
x
)
= +(hL
z
)
= hL
z
we derive that
[L
x
, L
+
] = hL
z
(6.57)
[L
y
, L
+
] = hL
z
(6.58)
[L
z
, L
+
] = hL
+
(6.59)
and its companion
[L
z
, L

] = hL
+
(6.60)
This last equation tell us that L
+
ladders us up, and L

ladders us down on L
z
components. If
L
z
| >= something| >
23
then
L

L
z
| >= somethingL

| >
or
[L
z
L

+ h]| >= somethingL

| >
L
z
L

| >= (something h)L

| >
which means that where ever we were, we are now lower
by h.
L

=
h
h
h
h
K
K h
K2
K3
K4
K5
FIG. 2: Laddering Down on the z-component of angular mo-
mentum
Next, we need an expression for L
+
L

, not the com-

mutator. It is:
L
+
L

= (L
x
+L
y
)(L
x
L
y
)
= L
2
x
+L
2
y
+(L
y
L
x
L
x
L
y
)
or
= L
2
x
+L
2
y
+L
2
z
+(L
y
L
x
L
x
L
y
) L
2
z
or
= L
2
x
+L
2
y
+L +z
2
+(hL
z
) L
2
z
i.e.
L
+
L

= L
2
+ hL
z
L
2
z
and repeating this for the other order, one has
L

L
+
= L
2
hL
z
L
2
z
If
L
z
| >= Kh| >
with no intentional restriction on the value of K, and
L
2
| >= K

h
2
L
+
| > (6.61)
L

L
+
| > + hL
z
| > +L
2
z
| >= K

h
2
| >
If this particular ket is the highest one, |hi >, then lad-
dering up on it must result in destruction, so we have
+ hL
z
|hi > +L
2
z
|hi >= K

h
2
|hi >
+(hi) h
2
|hi > +(hi)
2
h
2
|hi >= K

h
2
|hi >
which means that
+(hi) + (hi)
2
= K

while, working down from the low ket one has

L
+
L

|lo > hL
z
|lo > +L
2
z
|lo >= K

h
2
|lo >
which is
(lo) h
2
L
z
|lo > +(lo)
2
h
2
|lo >= K

h
2
|lo >
i.e.,
(lo) + (lo)
2
= K

which means
(lo) + (lo)
2
= K

= +(hi) + (hi)
2
= (lo)((lo) 1) = (hi)((hi) + 1)
which can only be true if (lo) = - (hi). Say (hi) = 7,
then K = 7*8 and -7(-7-1) which is the same! Note that
if (hi) = 7.1 then (lo) can not be achieved by stepping
down integral multiples of h.
24
VII. LAGUERRE POLYNOMIALS
The radial equation for the H-atom is

h
2
2
_
d
2
dr
2
+
2
r
d
dr

( + 1)
r
2
_
R(r)
Ze
2
r
R(r) = ER(r)
which we need to bring to dimensionless form before pro-
ceeding (text book form). Cross multiplying, and den-
ing = E we have
_
d
2
dr
2
+
2
r
d
dr

( + 1)
r
2
_
R(r)+
2Ze
2
h
2
r
R(r)
2
h
2
R(r) = 0
and where we are going to only solve for states with > 0,
i.e., negative energy states.
Dening a dimensionless distance, = r we have
d
dr
=
d
dr
d
d
=
d
d
so that the equation becomes

2
_
d
2
d
2
+
2

d
d

( + 1)

2
_
R()+
2Ze
2

h
2

R()
2
h
2
R() = 0
which is, upon dividing through by
2
,
_
d
2
d
2
+
2

d
d

( + 1)

2
_
R()+
2Ze
2
h
2

R()
2
h
2

2
R() = 0
Now, we choose as

2
=
2
h
2
so
_
d
2
d
2
+
2

d
d

( + 1)

2
_
R() +
2Ze
2

R() R() = 0
(7.1)
To continue, we re-start our discussion with Laguerres
dierential equation:
x
d
2
y
dx
2
+ (1 x)
dy
dx
+y = 0 (7.2)
To show that this equation is related to Equation 7.1 we
dierentiate Equation 7.2
d
_
x
d
2
y
dx
2
+ (1 x)
dy
dx
+y = 0
_
dx
(7.3)
which gives
y

+xy

+ (1 x)y

+y

= 0
which is
xy

+ (2 x)y

+ ( 1)y

= 0
or
_
x
d
2
dx
2
+ (2 x)
d
dx
+ ( 1)
_
dy
dx
= 0 (7.4)
Doing it again (dierentiating), we obtain
d (xy

+ (2 x)y

+ ( 1)y

= 0)
dx
which leads to
y

+xy

+ (2 x)y

+ ( 1)y

= 0
which nally becomes
_
x
d
2
dx
2
+ (3 x)
d
dx
+ ( 2)
_
d
2
y
dx
2
= 0 (7.5)
Generalizing, we have
_
x
d
2
dx
2
+ (k + 1 x)
d
dx
+ ( k)
_
d
k
y
dx
k
= 0 (7.6)
VIII. PART 2
Consider Equation 7.1
_
d
2
d
2
+
2

d
d
R()
( + 1

2
_
R()+
2Ze
2
h
2

R()R() = 0
(8.1)
if we re-write it as
_

d
2
d
2
+ 2
d
d

( + 1

_
R() +
2Ze
2
h
2

R() R() = 0
(8.2)
(for comparison with the following):
xy

+ 2y

+
_
n
k 1
2

x
4

k
2
1
4x
_
y = 0 (8.3)
Notice the similarity if x, i.e., powers of x, x
1
etc.,
2Ze
2
h
2

n
k 1
2
(8.4)

x
4
(8.5)
k
2
1
4x

( + 1)

(8.6)
We force the asymptotic form of the solution y(x) to
be exponentially decreasing, i.e.,
y = e
x/2
x
(k1)/2
v(x) (8.7)
25
and ask what equation v(x) solves. We do this in two
steps, rst assuming
y = e
x/2
w(x)
and then assuming that w(x) is
w = x
(k1)/2
v(x)
So, assuming the rst part of Equation 8.7, we have
y

(x) =
k 1
2
x
(k3)/2
w(x) +x
(k1)/2
w

(x)
and
y

(x) =
k 1
2
k 3
2
x
(k5)/2
w(x) +
k 1
2
x
(k3)/2
w

(x) +
k 1
2
x
(k3)/2
w

(x) +x
(k1)/2
w

(x) = 0
which we now substitute into Equation 8.3 to obtain
xy

=
k 1
2
k 3
2
x
(k3)/2
w(x) + (k 1)x
(k1)/2
w

(x) +x
(k+1)/2
w

(x)
2y

= 2
k 1
2
x
(k3)/2
w(x) + 2x
(k1)/2
w

(x)
ny = nx
(k1)/2
w(x)

k 1
2
y =
k 1
2
x
(k1)/2
w

x
4
y =
x
(k+1)/2
4
w

k
2
1
4x
y =
k
2
1
4
x
(k3)/2
w 0 (8.8)
or
xw

+ (k + 1)w

+
_
n
k 1
2

x
4
_
w = 0 (8.9)
IX.
Now we let
w = e
x/2
v(x)
(as noted before) to obtain
w

=
1
2
e
x/2
v +e
x/2
v

=
1
4
e
x/2
v e
x/2
v

+e
x/2
v

so, substituting into Equation 8.8 we have

xw

= e
x/2
_
x
4
v xv

+xv

_
(k + 1)w

= e
x/2
_

k + 1
2
v + (k + 1)v

_
_
n
k 1
2

x
4
_
w = e
x/2
_
n
k 1
2

x
4
_
v (9.1)
= 0 (9.2)
so, v solves Equation 7.6 if = n. Expanding the r.h.s.
of Equation 9.1 we have
x
4
v
x
4
+xv

+(k+1x)v

+
_
n
k 1
2

k + 1
2
_
v = 0
i.e.,
xv

+ (k + 1 x)v

+ (n k)v = 0
which is Equation 7.6, i.e.,
v =
d
k
y
dx
k
26
and
y = e
x/2
x
(k1)/2
d
k
y

dx
k
or
w

=
1
4
e
x/2
v e
x/2
v

+e
x/2
v

so, substituting into Equation 8.8 we have

xw

= e
x/2
_
x
4
v xv

+xv

_
(k + 1)w

= e
x/2
_

k + 1
2
v + (k + 1)v

_
_
n
k 1
2

x
4
_
w = e
x/2
_
n
k 1
2

x
4
_
v (9.3)
= 0 (9.4)
so, v solves Equation 7.6 if = n. Expanding the r.h.s.
of Equation 9.3 we have
x
4
v
x
4
+xv

+(k+1x)v

+
_
n
k 1
2

k + 1
2
_
v = 0
i.e.,
xv

+ (k + 1 x)v

+ (n k)v = 0
which is Equation 7.6, i.e.,
v =
d
k
y
dx
k
and
y = e
x/2
x
(k1)/2
d
k
y

dx
k
or
R() = e
/2

(k1)/2)
L
k
n
()
where y

and R() are solutions to Laguerres Equation

of degree n. Wow.
X. PART 3
Now, all we need do is solve Laguerres dierential
equation.
xy

+ (1 x)y

+y = 0
where is a constant (to be discovered). We let
y =
?

=0
a

and proceed as normal

xy

= 2a
2
x + (3)(2)a
3
x
2
+ (4)(3)a
4
x
3
+
+y

= (2)a
2
x + (3)a
3
x
2
+ (4)a
4
x
3
+
xy

= a
2
x (2)a
2
x
2
(3)a
3
x
3

+y = a
0
+a
1
x +a
2
x
2
+ = 0 (10.1)
which yields
a
1
= a
0
a
2
=
1
4
a
1
a
3
=
2
9
a
2
a
4
=
3
16
a
3
(10.2)
or, in general,
a
j+1
=
j
(j + 1)
2
a
j
which means
a
1
=

1
a
0
a
2
=
(1 )
(4)(1)
a
0
a
3
=
(2 )(1 )
(9)(4)(1)
a
0
a
4
=
(3 )(2 )(1 )
(16)(9)(4)(1)
a
0
(10.3)
which nally is
a
j
=

j1
k=0
(k )

j
k=1
(k
2
)
a
0
and
a
j+1
= (j )

j1
k=0
(k )
(j + 1)
2

j
k=1
(k
2
)
a
0
=
j
(j + 1)
2
a
j
which implies that
a
j+1
a
j
=
j
(j + 1)
2

1
j
as j . This is the behaviour of y = e
x
, which would
overpower the previous Ansatz, so we must have trunca-
tion through an appropriate choice of (i.e., = n

).
XI.
If were an integer, then as j increased, and passed
into we would have a zero numerator in the expression
a
j+1
=
(j )
(j + 1)
2
a
j
27
and all higher as would be zero (i.e., not a power series
but a polynomial instead)! But

2
=
2
h
2
=
2E
h
2
so, from Equation 8.6 we have
k
2
1
4
= ( + 1)
k
2
1 = 4
2
+ 4
k = 2 + 1
so
k
2
1
2
=
2 + 1 1
2
=
and therefore Equation 8.3 tells us that
_
n

k 1
2
_
= n

=
2Ze
2
h
2

implies
=
2Ze
2
h
2
(n

)
2

2
=
2E
h
2
=
Z
2
e
4
h
4
(n

)
2
i.e.,
E =
Z
2
e
4
2h
2
(n

)
2
[1] the only thing that happens in making the complex con-
jugate is that each is changed to (and each ).
[2] the bracket, hah, hah.
[3] notice the rewriting into momentum language!
[4] The limits correspond to = 0 to =