PH 4010: QUANTUM MECHANICS II (45L, 3C)

Dependencies: PH 3001 is strongly recommended

Syllabus: Wave packets; Momentum space wave function; Time variation of expectation values;
Ehrenfest's theorem; Virial theorem; Matrix representation of wave functions and operators; Time
evolution of a quantum system; Angular momentum: orbital angular momentum operator, eigenvalues
and eigenfunctions, matrix representations of angular momentum operators, spin angular momentum
operator and its general properties, addition of angular momenta; Approximation methods: time-
independent perturbation theory for non-degenerate and degenerate levels, fine-structure of one-
electron atoms, variational method, time-dependent perturbation theory for transitions induced by
constant and periodic perturbations, Fermi's golden rule; Several- and many-particle systems: systems
of identical particles and the physical meaning of identity, symmetric and anti-symmetric wave
functions and their construction from unsymmetrized functions, Fermi gas, Pauli exclusion principle,
two-electron atoms and application of approximation methods to obtain their ground and excited state
energies, L-S coupling and j-j coupling schemes for many-electron atoms; Interaction of one-electron
atoms with: electromagnetic radiation, constant external electric fields, constant external magnetic
fields; Introduction to quantum collision theory.

Assessment: Mid & End of semester written examinations

References: (1) Introduction to Quantum Mechanics D.J. Griffiths

(2) Introduction to Quantum Mechanics B.H. Bransden and C.J. Joachain
(3) Quantum Physics S. Gasiorowicz
(4) Quantum Physics M.S. Rogalski and S.B. Palmer
(5) Quantum Mechanics R.L. Liboff
(6) Quantum mechanics - P.J.E. Peebles

Quantum mechanical view point of classical mechanics

The Correspondence Principle describes the limit of transition from q. m. to c. m. According
to this principle, the motion of a wave packet agrees with that of corresponding classical
particle whenever the distances and momenta involved in describing the motion of the
particle are so large that the uncertainty principle may be ignored.

As we know, well-defined trajectories do not exist in q. m. Therefore, we cannot write down

the equations which give dr dt and dp dt like we could do in c. m. But, the so-called
Ehrenfests Theorem tells us that quantum mechanical equations reduce to classical forms
when the averages of respective quantities are taken. According to this theorem, Newtons
equation of c. m. are exactly satisfied by the expectation (average) values of the
corresponding operators in q. m. i.e., one can study the rate of change of expectation values

r and p in q.m.

Time variation of expectation values

Consider an observable A represented by the operator A . The expectation value of A in the

state (normalized to unity) is then A = A
 2

Since A has all its spatial dependence integrated out, it may be a function of time. The
time variation of the expectation value is given by
d A d A A
= = A + + A
dt dt t t t

Using the TDSE and its complex conjugate

i = H = H
t

i =H
t
d A 1 A 1
= H A + +
AH
dt i t i

Since H is Hermitian,
H A = H A H A = H A

d A
=
1 + A + 1 AH
HA
dt i t i

d A 1 A
=
H , A + ------------ (A)
dt i t

A d A 1
If A has no explicit time dependence, then = 0 = H , A
t dt i

Ehrenfest's theorem
Consider a particle of mass m moving under the influence of a potential V ( x) . The
p x2
Hamiltonian is then,= H + V ( x )
2m
x
(i) When A x = 0
t
d x i , x i p x2 ( x ) , x
Relation (A) = = H + V
dt 2m
Since V ( x ) , x = 0
d x i i
= = p x2 , x x , p x2
dt 2m 2m
d x i i
= [ x , p x ] p x + p x [ x , p x ] = 2i p x
dt 2 m 2 m
d x
1 dr p
= p x , is equivalent to the x-component of the classical equation = .
dt m dt m
 3

d r 1
= p is satisfied (for 3-d) in q. m.
dt m
p x
(ii) When A p x = 0
t
d p x i i p x2
Relation (A) = H=
, p x + V ( x ) , p x
dt 2m
Since p x2 , p x = 0
d p x i i
= V ( x ) , p x = p x , V ( x )
dt

To evaluate p x , V ( x ) , operate it on some function ( x )

p x ,=
V ( x ) ( x ) p xV ( x ) ( x ) V ( x ) p x ( x )

p x , V ( x ) ( x=
)
i x
( )
V ( x ) ( x ) V ( x ) p x ( x=
)
i x
V ( x ) ( x )

V ( x )
p x , V ( x ) =
i x
d p x dV ( x )
=
F ( x )
=
dt dx

The above relationship can be identified as being equivalent to the classical equation,
d px dV ( x )
= = F ( x ) , only if one can show that
dt dx
dV ( x ) dV ( x )
= F ( x )
=.
dx d x
Ehrenfest noted that the above equality holds approximately, (i) when V ( x ) varies slowly as
a function of x and (ii) if x is small, because
dV ( x )
F ( x) =
dx
(x )
2
x
F (=
x) F( x ) + (x x ) F ( x )+ F ( x ) + .....................
2!
(x )
2
If ( x ) =
2
x is small, by taking the average and neglecting the higher order terms

F ( x) F ( x ) + (x x ) F ( x )
dV ( x ) dV ( x )
F ( x) F ( x )
dx d x
d p x dV ( x )
=
F ( x ) ,
=
dt d x
 4

dp
which is equivalent to the x-component of the classical equation = V ( r ) = F (r )
dt

d p
V ( r ) = F ( r ) is satisfied (for 3-d) in q. m.
dt
d A 1 A
Consider the relation, = H , A + -------------- (A)
dt i t
A
If A has no explicit time dependence, then = 0.
t
d A i
Then, the rate of change of expectation value for any state = H , A
dt

In addition, if A commutes with H , then H , A = 0

d A
= 0
dt
The observable represented by A is a constant of the motion.

Eg: For a system having a time-independent Hamiltonian, with A H (here H t =0 )

H , H = 0 H = E is a constant of the motion.

(the analogue of energy conservation for conservative systems in c. m.)

For a free particle, with A p (here p t =0 )

p , H = 0 p is a constant of the motion.

A
Ex:- Show that, if H , A = 0 and = 0, then A is constant in time.
t
2
Hint: Use the fact that ( A ) = A 2 A and show that A2 and A are constant
2

in time.

Virial Theorem

Consider a particle of mass m moving in 1-d under the influence of a potential V ( x) . Let E
be an eigenfunction of the time-independent Hamiltonian H corresponding to the eigenvalue
E. a stationary state of the system is E ( x, t=
) E ( x) exp( iEt ) .
Then, for a time-independent operator A (then A t =0 ), the expectation value
d A
A = E A E = E A E does not depend on time. = 0
dt
Relation (A) E H , A E = 0 E H , A E = 0

Choose A x p x (or p x x ) H , x p x
= 0
 5
V
Expanding the commutator 2 T = x
x
, ( In 3-d, 2 T=
r .V )
px2
where T = is the kinetic energy of the particle.
2m
The above result is known as the virial theorem.
Note: If V is spherically symmetric and proportional to r s , for a stationary state of the system
V
= 2 T r
= s V .
r

Ex: Show that, when the initial state of a linear harmonic oscillator is not an energy
eigenstate, x and px exhibit harmonic motion with the classical frequency, thus,
confirming the Ehrenfests theorem.

p x2 p x2 1
For a linear harmonic oscillator, H = + V ( x) = + m 2 x 2 , - classical freq
2m 2m 2
From Ehrenfests equations
d x px
= ------------ (1)
dt m
d px V ( x ) 1 2 2
= = m x = m 2 x ------------ (2)
dt x x 2
d px
Differentiating equ.n (1) w.r.t. time and substituting for in equn (2)
dt
2
d x
2
+ 2 x =
0
dt
Assuming a solution of the form
= x a1 sin t + a2 cos t ------------- (3)
equ n (1) p=
x m a1 cos t m a2 sin t --------- (4)

t = 0),
Assuming that, initially (at = x x 0,
= px px 0
n n
equ. (3) x 0
= a2 , equ. (4) px 0
= m a1
px
=x 0
sin t + x = cos t A sin ( t + x )
m 0

2
px 0 2 m x
where A = + x , tan x =0 .
m 2 2 0
px 0
px 0 cos t m x 0 sin t =
px = B sin t + px ( )
2 2 px 0
where px 0 + m 2 x0 ,
B = tan px =

m x 0
x and px exhibit linear harmonic oscillator motion with classical frequency .
 6
Fourier Transforms

Any function f ( x ) defined for all real values of x , < x < , can be written as a Fourier
transform of another function g ( k ) ,

1
f ( x ) = ( 2 ) 2
g ( k ) exp ( ik x )dk

Then g ( k ) can also be written as a Fourier transform of f ( x ) ,

1
g ( k ) = ( 2 ) 2
f ( x ) exp ( ik x )dx

Note: A function f ( x ) can only be expressed as a Fourier transform if the above Fourier
integrals converge. This requirement is satisfied when f ( x ) and g ( k ) are square-
integrable functions.

2 2
i.e. f ( x ) dx < , g (k ) dk <

Momentum Space Wave Function

Consider the wave packet,

1 i p x E ( p ) t
( x , t ) = ( 2 ) 2
e ( p ) dp (1)

formed by superposing plane waves of different wave numbers. Such a wave packet
represents a particle confined to a certain spatial region of the x-axis. (Read also the note
given on page 8)

Here, p px and p = k and it can be either +ve or ve.

( p ) - amplitude of the plane wave corresponding to the momentum p. (generally complex

but consider the real case only)

Define ( x ) ( x, t =0 )

1
Equation (1) ( x ) = ( 2 ) 2
e
i px
( p ) dp ... (2)

( x ) is the Fourier transform of the momentum space wave function ( p ) .

The Fourier transform of the configuration (co-ordinate) space wave function ( x ) is given
by ( p ) as

1
( p ) = ( 2 ) 2
e
i p x
( x ) dx .. (3)

 7

and equation (3) holds for all types wave functions ( x ) . In momentum space, ( p ) plays
the role analogous to that of ( x ) in configuration space.
At time t, the wave function in the configuration space (see equation (1)) is given by the
Fourier transform of the momentum space wave function ( p, t ) as

1
( x, t )
= ( 2 ) 2
e
i px
( p, t ) dp .. (4)

iE ( p ) t
where ( p, t ) e
= (=
p) and ( p ) ( p, t 0 )

Fourier transform of ( x, t ) is given by ( p, t ) as

1
( p, t )
= ( 2 ) 2
e
i p x
( x, t ) dx (5)

Equation (5) holds for all types of wave functions ( x, t ) . It describes the momentum
distribution in a quantum state.

It can be proven that,

2
if ( x, t ) is normalized i.e. ( x, t ) dx =
1 ( p, t ) is also normalized.

( p, t ) =
* ( p, t ) ( p, t ) dp =
* ( p ) ( p ) dp
( p, t ) is the probability of finding at the time t the momentum of the particle lies within
the length element d p at the point p in the momentum space.

In k-space, equations (2) and (3) can be given in the forms,

1
( x ) = ( 2 ) 2
e
ik x
( k ) dk (6)


1
( k ) = ( 2 ) 2
e
i k x
( x ) dx (7)

Consider p defined in x-space

In x-space, the operator form of momentum, p = i .
x


( x, t ) p ( x, t ) dx = ( x, t ) i x ( x, t ) dx
* *
p =

Using the expression of ( x, t ) given by equn (4), it can be proven that

( p, t ) p ( p, t ) dp =
( p, t ) p ( p, t ) dp
* *
p =

Suggests that in p-space, the observable p should be associated with the multiplicative
operator p = p .

Consider x defined in x-space

 8

( x, t ) x ( x, t ) dx = ( x, t ) x ( x, t ) dx
* *
x =

Using the expression of ( x, t ) given by equ (4), it can be proven that

n

( ) p ( ) ( p, t ) x ( p, t ) dp
* *
x = p , t i p , t dp =

Suggests that in p-space, the operator associated with the observable x should be

x = i .
p

Note: The above relations for p and x can also be proven by using time-independent
wave functions ( x) and ( p ) given by equn.s (2) and (3).

Summary,

In x-space, the operator associated with position, x = x

In x-space, the operator associated with momentum, p x = i
x

In p-space, the operator associated with position, x = i
p
In p-space, the operator associated with momentum, p = p

Note:
Suppose we use the wave function, ( =
x, t ) {
A exp i k x ( k ) t to represent a free }
particle moving along the x-axis with a definite momentum p and an energy E. (the
2 p E
wavelength of the plane wave = , wave no. k = and angular frequency = ),
k
( x=
, t) {
A exp i px E ( p ) t . }
It will not satisfy the normalization condition

2
( x, t ) dx =
2


A

dx 1
2
Since ( x, t )
2
A , there is an equal chance of finding the particle at any point along the
=
x-axis. delocalized particle

The above plane wave describes the idealized situation of a free particle having a definite
momentum but which is completely delocalized. To avoid this difficulty of delocalization,
we can give up the requirement of precisely known momentum and superpose waves
corresponding to different momenta to form a localized wave packet which can be
normalized to unity. Such a wave packet presents a particle having a fairly precise value of
both momentum and position, and is given as

1 2 i p x E ( p ) t
( x , t ) = ( 2 ) e ( p ) dp .

 9

All the above definitions can be extended to 3-dimensions. The wave packet in 3-dimensions

i p. r E ( p ) t
( 2 )3 2
(r , t ) = e ( p ) dp ,


where d p = d px d p y d pz
At time t,

3
(r , t )
= ( 2 ) 2
ei p . r ( p , t ) d p


3
( p, t )
= ( 2 ) 2
e i p. r ( r , t ) d r ,

i E ( p ) t
(r , t )
where = e i Et ( r ) and
= ( p, t ) e ( p)

Defining, ( r ) ( r , t 0)
= ( p ) ( p, t 0 )
and =

3
( r ) = ( 2 ) 2 ei p . r ( p ) d p


3
( p ) = ( 2 ) 2
e i p. r ( r ) d r


If ( p ) is normalized to unity, then so is ( r ) , ( r , t ) and ( p, t ) .

( p, t ) =
* ( p, t ) ( p, t ) d p =
* ( p ) ( p ) d p

( p, t ) is the probability at time t that the momentum of the particle lies within the

momentum space volume element d p = d px d p y d pz about the point p px , p y , pz . ( )

( p, t ) plays in momentum space the role assigned to ( r , t ) in the configuration space.

The Schrodinger Equation in Momentum Space

( r , t ) satisfies the TDSE,
p 2
(r , t ) =
i H ( r , t ) , where H = + V ( r , t )
t 2m
To transform the above equation in momentum space, we first write
3 3 p 2
i ( 2 ) 2 ei p.r =

( r , t ) dr ( 2 ) 2 ei p.r + V ( r , t ) ( r , t ) d r
t 2m
2
p 3
i ( p, t ) = ( p, t ) + ( 2 ) 2 ei p.r V ( r , t ) ( r , t ) d r
t 2m
3
Since (r , t )
= ( 2 ) 2
e i p.r
( p , t ) d p
 10

p2 3 3
i ( p, t ) = ( p, t ) + ( 2 ) 2 ( 2 ) 2 e i p.r e + i p.r V ( r , t ) ( p , t ) d p d r
t 2m

p2
= ( p, t ) + ( 2 ) e (
3 i p p ).r
V ( r , t ) ( p , t ) d p d r
2m

By defining, ( 2 )3 ei( p p).r V ( r , t ) d r ,
V ( p p , t ) =

we get the Schrodinger equation in momentum space as

p2
i ( p, t ) = ( p, t ) + V ( p p , t ) ( p , t ) d p .
t 2m
Since the integral term is generally more complicated than the corresponding TDSE in
configuration space, the latter is used in most applications.

Tutorial 1
1. Consider a particle of mass m moving in a potential V(r, t), so that its Hamiltonian is given
p 2 d
by =H + V (r , t ) . Prove the result = A (i ) 1 [ A , H ] + A t and hence, prove
2m dt

d p d
the Ehrenfet equations r = , p = V . When proving that the Ehrenfest's
dt m dt
equations are equivalent to Newton's equations of motion one has to use the fact that F(x) =
F(x). Discuss under what circumstances this condition is approximately valid. Also prove
d 1
that x 2 = x + p x x ] .
[ xp
dt m

2. Determine the probability distribution for various values of momentum for the ground
state of a particle in an infinitely deep, asymmetric, square potential well of width L.
What is the probability that the particle will have a momentum in the range / L
to 2 / L ?

3. A particle has a wave function in the form of a Gaussian wave packet

(x) = (1/22)1/4exp{(xx 0 )2/42 + ik 0 x}. Calculate x, x2, p x , p x 2. Show that
(x)(p x ) has the minimum value for this wave packet. ((O)2 = O2 O2).

x / (2 x )
4. Consider the wave packet given by ( x) = Cei p0 x / e , where C is a normalisation
constant. Obtain the corresponding momentum space wave function ( px ) and verify that it
is normalized to unity. Suggest a reasonable definition of the width of the momentum
distribution and show that xpx ~ .

5. The ground state (1s) wave function (in co-ordinate space) is given by
= (r ) (1 a )
3 12
exp ( r a ) . Evaluate r , r 2
for the electron. Find the
momentum distribution of the electron in the ground state and use this to evaluate
p , p 2 . Hint: To simplify your integral in the Fourier transform, choose the z-axis to
be parallel to the momentum. Repeat your work with the 2s wave function.
 11

Time Evolution of a Quantum System

Consider the TDSE

(r , t ) p 2
i = H (r , t ), + V (r ) H
where =
t 2m

When the potential is time-independent, the general solution (r , t ) of the TDSE can be

(
expanded in terms of energy eigenfunctions solutions of the TISE H E ( r ) = E E ( r ) as )

CE ( t ) E ( r )
(r , t ) =
E

The expansion coefficients CE ( t ) depend on time. The particular solutions of the TDSE are

the stationary states

t ) E ( r ) exp ( i Et )
E (r ,=

To obtain an expression for CE ( t ) , multiply (r , t ) by *E ( r ) and integrate over a large

volume.

E ( r ) (r , t )d r
*
CE ( t ) E* ( r ) E ( r ) d r
=
E

= CE ( t ) E E (using othonormality of E ( r ) )
E
= CE ( t )

CE ( t )
= E ( r ) (r , t )d r
*

CE ( t ) E ( r ) back in the TDSE
By substituting the solution, (r , t ) =
E

i
t E
CE ( t ) E ( r ) = H CE ( t ) E ( r )
E

= C ( t ) H ( r )E E
E

= CE ( t ) E E ( r )
E

Multiplying both sides by E* ( r ) and integrating over a large volume,

i
t E
CE ( t ) E* ( r ) E ( r ) dr = CE ( t ) E E* ( r ) E ( r ) dr
E

i CE ( t ) = E CE ( t )
t

Solution C
= E (t ) CE ( t0 ) exp i E ( t t0 )
 12

(r , t )
= CE ( t0 ) exp i E ( t t0 ) E ( r ) ,
E

= CE E ( r ) exp [ i E t ] ,
E

= CE E ( r , t ) ,
E

where CE = CE ( t0 ) exp [ i E t0 ] .

The above solution has been expressed as a linear superposition of stationary states

( E ( r, t ) ) as required by the superposition principle.

The coefficient CE can be evaluated by knowing ( r , t ) at any particular time t0 , because
* *
CE (t ) = E ( r ) ( r , t ) d r CE (t0 ) = E ( r ) ( r , t 0 ) d r

=CE exp ( i E t0 ) E* ( r ) ( r , t0 )d r

(r , t ) = CE E ( r , t ) = CE E ( r ) exp ( i Et )
E E

(r , t )
= E* ( r ) ( r , t0 ) dr exp iE (t t0 ) E ( r )
E

This expression gives ( r , t ) at any time t , once it is known at t = t0 (usually t0 is taken to

be zero). It gives the time evolution of the wave function of a system when the potential and
hence H is time-independent.
In Dirac notation,

( t )= E (t0 ) exp i E (t t0 ) E
E

Unitary Transformation
Application of Unitary operator U for which U
=(
U U
= U )
I on any wave function is

known as a unitary transformation.

Let and be two wave functions of some states of a system and A be a linear Hermitian

operator such that A = .

Applying a unitary operator U on and ,

= U
= , U .
and provide completely equivalent description of the states as do and .
 13

Writing A =

A U = U A
U = A U =
U A

Since U
= U U
= U I

=A U
= A U , A U A U
Using unitary transformations, the following results can be proven
(1) If A is Hermitian, then A is also Hermitian.
(2) (i) Operator equations such as
= A C1 B + C2 C D , where C1 and C2 are constants

and B , C and D are operators, remain unchanged.

i.e.
= A C1 B + C2 C D , where A , B , C and D are transforms of

A , B , C and D .

(ii) If A and B are two operators such that A , B = C , where C is complex number

A , B
and A and B are their transforms, then=
=
A , B C .

(3) Eigenvalues of A are the same as those of A . i.e. If A n = an n , then

A n = an n , =
where n U=
n, A U AU
.

(4) The quantities A are unchanged under unitary transformations.

i.e. A A

When = , A A

Expectation values remain unchanged under unitary transformations.

When A
= I,

Scalar product is invariant under unitary transformation.

Since the Physical quantities such as eigenvalues, expectation values can also be obtained
from the transformed wave functions and operators, it may be easier to solve the problem by
finding a suitable unitary transformation leading to new sets of wave functions and operators.
Matrix representation of wave functions and operators
Consider a set of orthonormal functions { n } , i.e. n m = n m

Any wave function can be expressed in terms of this set, = cn n , where cn are
n

determined by cn = n .
 14
Since for a given set of functions { n } , the numbers cn specify completely, cn are said to

represent in the basis { n } .

[Equivalently, we represent any vector r in terms of the component vectors along a set of

orthogonal axes, r = c1 i + c2 j + c3 k , where cn ( n = 1, 2, 3) give the component

r along the each of the axes. =c1 i=
. r , c2 . r , c3 k . r ]
j=

Consider the action of a linear and Hermitian operator A on to produce .

= A .

Then can also be expanded in terms of the basis { n } .

=
= d m m , where d m m
m

=dm m A
= m A n cn
n

dm = Am n cn
n

The quantities Am n = m A n are called the matrix elements which give the matrix

representation of A in the basis { n } .

The equation d m = Am n cn relates the coefficients cn and d m which uniquely define

n

and and is completely equivalent to the operator equation = A . Therefore, Am n is

completely specify A within the basis { n } .

The equation d m = Am n cn ( = A ) can be written as a matrix equation

n

d = Ac ,

d1 A11 A12 . . c1

d 2 = A21 A22 . . c2
,
. . . . . .

. . . . . .

where d and c are column matrices (vectors) and A is a square matrix. The dimensions can
be finite or infinite.
*
c=
n n , dn
= n d=
n n
 15
The scalar product

= I
= n =
n dn* cn
= d c ,
n n

where c is a column vector with elements cn and d is a row vector with elements d n* .

c1

c
= d1* ( d 2* )
. . 2
.

.

Matrix properties and definitions

Two matrices A and B can be added when they have two equal numbers of rows and columns.
Addition is commutative, A + B = B + A
If C
= A + B is the matrix sum, then C=
mn Am n + Bm n

If C = A B is the matrix product, then Cm n = Am k Bk n which requires the number of

k

columns of A = number of rows of B.

Multiplication is distributive A ( B + C ) = A B + AC

Multiplication is associative A ( B C ) = ( A B)C

B A, then A and B are said to commute.
In general AB B A, and if AB =

The inverse A1 of A is such that A

= A1 A
= 1
A I , where I is the unit matrix,

I m n = m n. A matrix which possesses an inverse is said to be non-singular. The matrix AT

is the transpose of A if (A )
T
mn
= An m

( ) (A )
*
T
A is the adjoint of A if A = A
=*
nm
mn mn

A matrix is Hermitian, if A = A so that Am n = An* m .

If U 1 = U , then U is said to be a unitary matrix U

= U U
=
U I.

Trace of a matrix A=
, Tr A
= Am m sum of its diagonal elements
m

Consider the matrix element Am n corresponding to a Hermitian operator A . i.e. A = A ( )

=Am n m A n
= m A n
= (=
A ) m n n A m
=
*
An* m

The matrix A representing A is a Hermitian matrix. Similarly, it can be proven that.

 16
A unitary operator is represented by a unitary matrix.
Operator sum A + B is represented by a matrix sum A + B .

Operator product C = A B is represented by matrix product C = A B .

A square matrix A is said to be diagonal if it has non-vanishing elements only when m = n .

Consider the set of orthonormal eigenfunctions { n } of an observable A corresponding to

the eigenvalue an . A n = an n

The elements of the matrix A in the basis { n } (which is called the eigenbasis of A ) are

=Am n = m A n an m n
= an m n

the matrix representing A is diagonal with the diagonal elements being the
eigenvalues of A .

Let A be the matrix representing the observable A in a given basis { n } . Then the matrix

eigenvalue equation equivalent to A n = an n becomes A un = an un , where un is called

an eigenvector of the matrix A , belonging to the eigenvalue an .

If A is a physical observable, then A is Hermitian and the matrix A becomes Hermitian

and the eigenvalues an of the matrix equation Aun = an un , are real. They are given by the

Secular equation, A an I =
0

Note: un and A satisfy all the requirements of n and A . (orthogonality condition,

normalization condition etc.)
When the basis { n } consists of an orthonormal set of eigenfunctions of A , the matrix A
takes the diagonal form. Then, the normalized eigenvector un has all the elements zero
except for the nth element which is unity.

Eg: Algebraic method for obtaining the energy eigenvalues of a linear harmonic oscillator
(Refer PH 3001 lecture notes.)

p 2 p 2 k
Hamiltonian H = x + 1 k x 2
2
=x + 1 m 2 x 2 ,
2
=
2m 2m m
m i p x
Introducing the operators as done by Dirac a = x , using the
2 2 m
facts that p x and x are hermitian operators and that [ x , p x ] = i , it can be shown that
 17

a+ = a , a = a+ and [ a , a+ ] = 1

H
=
2
( a a+ + a+ =
a ) ( 1
a a+ =
2 ) (
a+ a + 1
2 )
H , a = a

If is an eigenvector of H belonging to the eigenvalue E, ( i.e. H = E ),

then we proved that a is also an eigenvector of H corresponding to the eigenvalue
( E ) .

a+ and a are called the raising and lowering operators respectively.

If E0 is the smallest eigenvalue and 0 is the corresponding eigenvector (i.e.

H 0 = E0 0 ) E0 = 12 .. Zero-point energy

Taking a+n 0 En , we could obtain H n = En n .

n and ( E0 + n ) =
E=
n ( n + 12 ) , where n = 0, 1, 2, 3, . . . . . . . . . .
If n be a normalized eigenvector corresponding to the eigenvalue En and n +1 be
a normalized eigenvector corresponding to the eigenvalue En +1 .
n +1 = Cn +1 a+ n
We have shown that the normalizing coefficient C
= n +1 1 n + 1.
Similarly, when n 1 = Cn 1 a n , it was shown that Cn 1 = 1 n.
[Ex: Prove all the above two results.]

The eigenvectors n with n = 0, 1, 2, 3, . . . . . . . . . . form an orthonormal basis

{ n } , where m n = m n .
Let us find the matrix representations of H , a+ and a in the orthonormal basis
{ n } with n = 0, 1, 2, 3, . . . . . . . . . .

H m=
n m H n= En m n= ( n + 12 ) m n ,
where m, n = 0, 1, 2, 3, . . . . . . . . . .

1 0 0 0 . . .
2

0 23 0 0 . . .
H = 0 0 52 0 . . .

0 0 0 72 . . .
. . . . . . .

 18

H is a diagonal matrix with elements ( n + 1

2 ) , n = 0, 1, 2, 3, . . . . . . . . . . .

( a+ )m n m a+ n =
= n + 1 m n +1 =
n + 1 m, n + 1 ,

where m, n = 0, 1, 2, 3, . . . . . . . . . .

0 0 0 0 ...

1 0 0 0 ...
a+ = 0 2 0 0 ...


0 0 3 0 ...

. . . . . . . .

a+ is a real matrix with only the elements below the diagonal are non-zero.

( a )m n
= m a n
= m n 1
n= n m, n 1 ,

where m, n = 0, 1, 2, 3, . . . . . . . . . .
0 1 0 0 ...

0 0 2 0 ...
a = 0 0 0 3 ...


0 0 0 0 ...

. . . . . . . .

a is a real matrix with only the elements above the diagonal are non-zero.

By definitions of a , the matrix representations of x and p x can be obtained.

m
=x ( a+ + a ) =p x i ( a+ a )
2 m 2

=xm n m x n
= m ( a+ + a ) n
2 m

=

2 m
( n + 1 m n +1 + n m n 1 )
=

2 m
( n + 1 m, n + 1 + n m, n 1 )
m
( px )m n
= m p x n
= i m ( a+ a ) n
2
m
=i
2
( n + 1 m n +1 n m n 1 )
m
= i
2
( n + 1 m, n + 1 n m, n 1 )
 19

0 1 0 0 ... 0 1 0 . ...

1 0 2 0 ... 1 0 2 . ...
m
x = 0 2 0 3 ..., px i 0 2 0 3 ...
2 m 2
0 0 3 0 ... 0 0 3 0 ...

. . . . . . . . . . . . . . .

In the matrix elements xm n and ( p x )m n , by setting m = n , one can show that the
average values x and px are equal to zero. Using the operators a and a and
following the same procedure used to obtain xm n and ( p x )m n , one can show that
m
=x2 ( 2n + 1) and
= px2 ( 2n + 1) . Then, the product x. px can be
2 m 2
evaluated and prove that the H.u.p. is satisfied for the nth energy level.

Diagonalization of a matrix

Consider a matrix of rank 3, representing a Hermitian operator A in the orthonormal basis

{ 1 , 2 , 3 } .
A11 A12 A13

A = A21 A22 A23
A A32 A33
31
Suppose we want to transform the above matrix into a diagonal one. i.e. Dmn = Dnn mn .

D11 0 0

D = 0 D22 0
0 0 D33

Let U be a unitary matrix which transforms A into D via a unitary transformation.

i.e. U AU =D AU =U D U U
(since U= = U I )

3 3 3
Am nU n k
= U m n Dn k
= U=
m n Dk k n k U m k Dk k
=n 1=n 1=n 1
Am1 U1k + Am 2 U 2 k + A=
m 3 U3k U m k Dk k (m, k 1, 2, 3)
=

Setting k = 1, we get three linear homogeneous equations for m = 1, 2, 3 as given below.

A11 U11 + A12 U 21 + A13 U 31 =

U11 D11
A21 U11 + A2 2 U 21 + A2 3 U 31 =
U 21 D11
A31 U11 + A3 2 U 21 + A33 U 31 =
U 31 D11
 20
A11 D11 A12 A13
By eliminating U11 , U 21 and U 31 A21 A22 D11 A23 0
=
A31 A32 A33 D11

If we set k = 2 and k = 3, we get two similar determinantal equations with D11 replaced by
rd
D2 2 and D33 respectively. Therefore, we see that all D11 , D2 2 and D33 are roots of the 3
order characteristic equation in n (n = 1, 2, 3).
A11 n A12 A13
A21 A22 n A23 0
=
A31 A32 A33 n

For each eigenvalue (i.e. for D11 , D2 2 and D33 ), the three sets of simultaneous equations can
be solved to obtain U11 , U 21 , U 31 , U12 , U 2 2 , U 3 2 and U13 , U 2 3 , U 33 .
i.e. corresponding to each eigenvalue of A, we get a column vector as its eigenfunction.
Therefore, in the basis { 1 , 2 , 3 } , the unitary matrix U is built out of these three column
vectors as
U11 U12 U13

U = U 21 U 22 U 23
U
31 U 32 U 33

0 1 0

Eg.: Solve the eigenvalue problem
= for the matrix A 1 0 0 , with a 1 .
0 0 a

pn

Eigenvalue equation
= A Un =
n U n , where U n qn and n = 1, 2, 3.
r
n
n 1 0
Characteristic equation A n I = 1 n 0 = 0
0 0 a n
(a ( )
n ) n2 1 =0 1 = a, 2 = 1 and 3 = 1

Substituting each n into the matrix eigenvalue equation

0 1 0 p1 p1 p1

n =1 1 0 0 q1 = a q1 , eigenvector U1 = q1
0 0 a r r
1 r1 1

q1 a=
p1 p 0 0
p1= a 2 p1 1
p1 aq
=1 q1 0 U1 0
=
a r= ar1 r1= ? r
1 1
Using the normalization condition,
 21
0 0
U1 U1 = 1 (0 0 r1* )
0 =1
2
r1 =1 r1 =1 U1

= 0
r 1
1

(assuming r1 as real and positive)

1 1
1 1
Following the same procedure, it can be shown that, U 2 = 1 , U= 1
2 2
3

0 0

It is possible to show that the above U1 , U 2 , and U3 are orthogonal to each

other. Therefore, they form an orthonormal basis.
The unitary matrix that diagonalizes the matrix A can be written as
0 1 2 1 2

=U 0 1 2 1 2

1 0 0

a 0 0

Also, it satisfies the requirement
U AU = D , where D = 0 1 0 .
0 0 1

The treatment of Hydrogenic atom in the centre of mass co-ordinate system

A Hydrogenic atom contains an atomic nucleus of charge + Ze and an electron of charge e .
Eg.: H, He+ , Li ++
,......

In the previous work on hydrogenic atoms, it was assumed the mass of the nucleus to be
infinitely large when compared to the electron mass so that the nucleus remains fixed in
space (at the origin). This is a good approximation even for hydrogen, because
mnuc 2000 me . However, for a better agreement of the theoretical results with accurate
spectroscopic data, it requires the nuclear mass to be taken into account as finite. In such a
situation, the electron and the nucleus revolve around their common centre of mass point.

me electron

r= r1 r2
r1

M Nucleus

r2
0
 22

Z e2
The associated Coulomb potential is V ( r ) = , where r is the distance between
( 4 o ) r
the two particles.
Since V ( r ) depends on the relative co-ordinate r of the two particles, it is convenient to work

in the centre of mass (C.M.) frame of the two-particle system in which the total momentum

P is zero.
The Hamiltonian of the atom,
p12 p 22

H = + + V ( r1 r2 ) , p1 = i r1 , p 2 = i r2
2 me 2M

2 2 2 2
H = r1 r2 + V ( r1 r2 )
2me 2M

( r1 , r2 , t ) 2 2 2 2
TDSE i =
r1 r2 + V ( r1 r2 ) ( r1 , r2 , t )
t 2 me 2M
To simplify the problem, the system is changed from the laboratory frame to the C.M. frame.

me r1 + M r2
The position of C.M. is R = .
me + M


( )
Changing the variables from ( r1 , r2 ) to r , R , it can be shown that

2 2 2 2 2 2 2 2
r1 r2 = R r ,
2me 2M 2M 2

where M = me + M total mass of the particles

me M
= reduced mass of the particles.
me + M

(
r , R, t ) 2 2 2 2
TDSE i = R r + V ( r ) r , R, t ( )
t 2M 2

If V ( r ) is independent of time, the time dependence in the wave function can be separated

from the spatial part and then, the spatial part can be separated into product functions of

R and r .

(
r, R, t = )
( )
R ( r ) exp [ i ETot t ] ,

( )
where R and ( r ) satisfy the TISEs.
 23

2 2

2M
R R=( ) EC M R( ) - describes the motion of the C.M. as a free

particle of mass M and energy EC M .

2 2
r + V ( r ) ( r ) =E ( r ) - describes the relative motion of the two particles
2
as being equivalent to the motion of a particle

having a mass in the potential V ( r ) .

ETot
= EC M + E

As shown above, the original two-body problem has been decoupled into two one-body
problems, which are
(1) the free particle (C.M.)

(2) the single particle of mass in the potential V ( r ) .

Therefore, by working in the C.M. frame, the one-body Schrodinger equation of the relative
motion can be used to describe the Hydrogenic atom.
2 2 Z e2 Z e2
( r ) = E ( r ) , where V ( r ) =
2 ( 4 0 ) r ( 4 0 ) r
So, we have been able to show that the electron moves around the nucleus as though the
nucleus is fixed and the mass of the electron is slightly reduced to a value called the
reduced mass of the system. The equation of motion of the electron-nucleus system is in the
same form as the one we have considered before in PH 3001 course, if we simply substitute
in that for me . Since the above potential is central, we use spherical polar co-ordinates.

r
O y
Q
x
The Cartesian co-ordinates (x, y, z) of the point P and the spherical polar co-ordinates (r, , )
are related by
 24
x = r sin cos , y = r sin sin , z = r cos ,

where 0 r , 0 , 0 2 .

In spherical polar co-ordinates (r , , ),

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

d r d3 r = r 2 d r sin d d = r 2 d r d, where d = sin d d

2 2 2 1 2 L2 Z e2
H = + V (r ) = r 2 2
2 2 r 2 r r r (4 0 ) r
1 1 2
where L2 = 2
sin + is identified as the square of the
sin sin 2 2
orbital angular momentum of the electron

TISE, H (r ) = E (r ) , for the electron reads,
2 1 2 L2 Z e2
2 r (r ) =
E (r )
2 r r r 2 r 2 (4 0 ) r

Energy eigenfunctions

By Separating variables of the Schrodinger equation in spherical polar co-ordinates, it can be

shown that the spatial wave functions for hydrogenic atoms should be labeled by three
quantum numbers n, l and ml as

nl ml (r ) = Rn l (r ) Yl ml ( , ) .

The normalized angular part Yl ml ( , ) (spherical harmonics) of the wave function

n l ml (r , , ) can be written as
1
(2l + 1)(l ml )! 2
ml
Yl m ( , ) = (1) ml
Pl (cos ) ei ml ,
l
4 (l + ml )!

In Dirac notation, Yl ml ( , ) l ml Yl*ml ( , ) l ml

Spherical harmonics satisfy the orthonormality relation

2
* *
Yl ml ( , )Yl ml ( , ) d
= =
Yl m ( , )Yl m ( , ) d sin d
l l
l l ml ml
0 0

In Dirac notation, the orthonormality condition, l ml l ml = l l ml ml

 25

It has been proven that L2 , L z = 0 and the simultaneous eigenfunctions of L 2 and L z

are Yl ml ( , ) .
L2 Yl ml ( , =
) l (l + 1) 2Yl ml ( , ) L z Yl ml ( , ) = ml Yl ml ( , )

We designate the orbital angular momentum states corresponding to

l = 0, 1, 2, 3, .............. by the s, p, d, f, . (sub shell system of atoms)

l 0 1 2 3
Designation s (sharp) p (principal) d (diffuse) f (fundamental)

For s- states, l=0 0 ml 0 ml = 0 (one value)

For p- states, l=1 1 ml 1 m l = 1, 0, 1 (three values)

For d- states, l=2 2 ml 2 m l = 2, 1, 0, 1, 2 (five values)

For f- states, l=3 3 ml 3 m l = 3, 2, 1, 0, 1, 2, 3 (seven values)

We see that, for different l values, the spherical harmonics represent different orbital angular
momentum states possible for a particle.

When the hydrogenic atom is treated in the C. of M. frame, we simply have to replace me by
me M (4 0 ) 2
and a0 by a in relevant expressions, where = and a = .
me + M e2
Normalized radial eigenfunctions for the bound states of hydrogenic atoms are given as
3 1 2
(n l 1)!
2Z 2 l +1
Rn l (r ) = e 2 . l L n + l ( )
2 n [(n + l )!]3
n a

Using the above expression, the first few radial eigenfunctions can be written as follows.
( ) ( )
32
When n = 1 l=0
= R10 (r ) 2 Z a exp Z r a

( ) (1 Z r 2 a ) exp ( Z r 2 a )
32
When n = 2 l = 0 and 1 R20 (r ) = 2 Z 2 a
1
( ) ( Z r a ) exp ( Z r 2 a )
32
=R21 (r ) Z 2 a
3

When n = 3 l = 0, 1 and 2 R30 (r ) = ..... , R31 (r ) = ...... , R32 (r ) = ......

We can use the known expressions of Rn l (r ) and Yl ml ( , ) in nl ml (r ) = Rn l (r ) Yl ml ( , )
to write down the wave functions of first few states of hydrogenic atoms as follows.
 26

n=1 l=0 ml = 0 Y0 0 ( , ) = 1 4
1

( Z a ) ( )
32

= 100 (r ) exp Z r a

n=2 l=0 ml = 0 Y0 0 ( , ) = 1 4
1

( Z a ) (1 Zr 2a ) exp ( Z r )
32
200=
(r ) 2 a
2 2
3
l=1 ml = 0 Y10 ( , ) cos
4
1

( Z a 0 ) ( Zr a ) exp ( Z r )
32

= 210 (r ) 2a cos
4 2
3
ml = 1 Y1 1 ( , ) sin exp ( i )
4
1

( Z a ) ( Z r ) ( )
32
=
21 1 (r ) a exp Z r 2a sin exp ( i )
8

Energy Levels
By solving the TISE for a hydrogenic atom, the allowed bound state energy eigenvalues of
the electron can obtained as
2
Z e2 1 E1
En =
2 2 = 1, 2, 3, .............. (For hydrogen E1 = 13.6 eV )
, n =

2 4 0 n n2
e2 Z2
The energy values can also be given in the form, En = ,
(4 0 ) a 2 n 2
4 0 2 n2 a n 2
The radii of Bohr orbits are=
given by an = 2

e Z Z

As n takes on values 1, 2, 3, ............., , bound state energy spectrum of hydrogenic atoms

2
m Z e2
contains an infinite number of discrete levels from E1 = e2
to zero.
2 4 0
Spatial wave functions of different states in hydrogenic atoms are labeled by three quantum

numbers n, l and ml as nl ml (r ) = Rn l (r ) Yl ml ( , ) .
The total degeneracy of the energy level (without taking electron spin into account) En , is n 2 .
The hydrogenic energy levels depend on n and are independent of l and ml . The degeneracy with
respect to ml is present for any central potential. But, the degeneracy with respect to l is a
characteristic of the Coulomb potential. (i.e. V (r ) 1 r ).

= n 1, 2, 3, .............., and n is called the principal quantum number. It characterizes

atomic energy levels (or shells K, L, M, N, ........ designated for n = 1, 2, 3, ....... ) as given
by En with a degeneracy of n 2 , when V(r) is purely Coulombic (central).
 27
l 0, 1, 2, 3, .............., n 1 is called the orbital quantum number. For a given value of
n, there should be a n number of values of l. It characterizes orbital angular momentum states
or sub shells s, p, d, f, . designated for l = 0, 1, 2, 3, ..... .. When V(r) is modified to become
a non-Coulombic potential, the electron energy becomes dependent on l in addition to n , and gives
rise to n no. of distinct energy levels as En l , by removing the degeneracy only partially.

ml = 0, 1, 2, 3, ........, l is called the orbital magnetic quantum number.

( l ml l ) For a given value of l, there should be (2l + 1) number of values of ml . It
characterizes energy levels when they are subdivided in the presence of strong external
magnetic fields by removing the degeneracy totally.

In summary, the TISE for a hydrogenic atom can be written as

2 2 Z e2 E1
H=
(r ) E (r ) nl=
ml ( r ) En nl ml (r ) , where En =
2 (4 0 ) r n2

n = 1, 2, 3, ..........

In Diracs notation, nl m (r , , ) n l ml
l

Spectroscopically, atomic states are labeled as n l . Eg: 1s, 2s, 2p, 3s, 3p, 3d, ..

For an electron in a stationary state nl ml (r , , ) ,

2 2
Position Probability Density = nl ml (r , , ) = Rn l (r ) 2 Yl ml ( , )

Prob. of finding the electron in the volume element dr at the point r = nl ml (r , , ) 2 d r

Probability of finding the electron within a unit length at a distance r in any direction from
the nucleus (i.e. within a shell of radius r and of unit thickness) is given by the Radial
Distribution function, Dn l (r ) = r 2 Rn2l (r )

We designate the states corresponding to l = 0, 1, 2, ....... by the symbols

s, p, d , f , g , ...... When there is more than one particle, we have L = 0, 1, 2, ........ as the
total angular momentum quantum number and S , P, D, F , G are used to designate their
states.

Note also that,

th e2 Z2
Ionization potential in the n shell, =
IP En
=
(4 0 ) a 2 n 2
m l ml
Rn l (r ) Yl l ( , ) =
nl m (r , , ) =
R ( r )( 1) Yl ( , )
l n l
 28

(1)l nl m (r , , )
nl m (r , , ) = nl ml s have the parity of l.
l l

Eigenfunctions nl ml (r , , ) form an orthonormal basis as given by

*
n l m (r ) n lm (r ) d r = n n ll ml ml or equivalently n l ml n l ml = n n ll m
l l l
ml

Once nl ml (r ) and En are known, a particular solution to the TDSE is given by

nl ml (r )ei En t /
(r , t ) =

Tutorial 2
E ia
6. Find the eigenvalues and corresponding eigenvectors of the matrix 1 , where E 1 ,
i a E2
E 2 , a > 0. (Hint: To simplify your answers use the substitution, tan = 2a/(E 1 E2 ).).

7. For a non-interacting two-particle system with masses m 1 and m2 , the simple Hamiltonian
p12 p2
can be written as = H + 2 . If (x 1 , x2 ) is the wave function of the two-particle
2m1 2m2
system and E is the corresponding energy, find their values in terms of single particle wave
functions 1 (x 1 ) and 2 (x 2 ) and the corresponding energies E 1 and E2 . [Hint: Write (x1 ,
x 2 ) = 1 (x 1 ). 2 (x 2 ) and E = E 1 + E2 and substitute in TISE.] Rewrite the solutions using
the co-ordinates x = x1 x 2 and X = (m1 x1 + m2 x2 )/(m1 + m 2 ) which are the separation
between particles and the center of mass co-ordinates respectively and K = k 1 + k 2 and k =
(m 2 k1 + m1 k2 )/(m1 + m 2 ) which are the wave numbers corresponding to the total
momentum and the relative momentum. Here k 1 and k 2 are the wave numbers
corresponding to the single particle momenta as related to E1 and E2 by
2m1E1 2m2 E2
= k12 = 2
and k22 . Repeat your derivation when a potential V(x1 x 2 ) is acting
2
on the particles.

8. A system consists of two particles of masses m1 and m 2 , moving in an unbounded region of

constant potential. Their interaction can be described by means of a potential that is a
function only of the distance between the particles. (a) Write the Hamiltonian for the system
in terms of r 1 and r 2 , the position vectors of the two particles. (b) Introduce the new
coordinates: R, the position vector of center of mass of the system, and r, the position of
particle 2 relative to particle 1. Show that the Schrodinger equation can be separated in these
new coordinates. (c) Solve the equation for the motion of the center of mass. (d) What is the
physical interpretation of these eigenfunctions ?

9. Two masses, m 1 and m2 , which are restricted to move in a plane are connected by a massless
rod of length R to form a rigid rotator. (a) Set up the Schrodinger equation for this rotator
and obtain equations for the energy eigenvalues and the normalized eigenfunctions. (b)
Obtain an equation for the eigenvalues of the operator L2 = 22/2, which corresponds to
the square of the angular momentum of the rotator. (c) What is the expectation value of the
angular momentum for the state of the lowest energy for the rotator ? For a state having the
 29
energy E = m22/2I with m 0 ?

10. Consider a particle of mass m confined to the infinite spherical potential well, which is
0, if r < a,
defined as V (r ) = For this particle, show that the modified radial
, if r > a.
d 2 u (r ) l (l + 1) 2
2 2 mE
equation takes the form = 2 k u (r ) , where k = . (Since the
dr 2 r 2
potential is central, the angular part of the wave function is Yl ml , the same as before.)
Then, for the case that l = 0, obtain the energy eigenfunctions and corresponding energy
eigenvalues.

Matrix representations of angular momentum operators

For convenience, define two operators, L
= L x i L y

In spherical polar co-ordinates L= ei + i cot

Show that

(1) L2 , L = 0 (2) L L = L2 L2z L z (3) L + , L = 2 L z

(4) L z , L = L =
(5) L+ and L
L= L + , . ( i. e. L + and L are not Hermitian )

Consider the orbital angular momentum state of a particle, characterized by l and ml , which

is l , ml . Then,

L 2 l m=
l l ( l + 1) 2 l ml L z l ml = ml l ml

(
L2 L l ml ) = L L2 l ml (From Result (1))

(
L 2 L l ml ) = L l ( l + 1) 2 l ml

(
L 2 L l ml ) = (
l ( l + 1) 2 L l ml )
Therefore, L l ml has the same eigenvalue l ( l + 1) 2 as does l ml .

(
L z L l=
ml ) ( L L L ) l m z l (From Result (4))

L ( L
z l m ) = m L l m L
l l l l ml

L ( L
z l m ) = ( m 1) ( L l m )
l l l
 30

Therefore, L l ml is an eigenstate of L z with the eigenvalue ( ml 1) .

Therefore L + L ( ) increases (decreases) the z-component of the orbital angular momentum

by 1 unit ( ) and is called the raising (lowering) operator. i.e., if L l ml = l ml , then

l
l = l and m= ml 1 , and this process repeats after each operation of L .

Since L 2 = L x 2 + L y 2 + L z 2 L 2 L z 2 = L x 2 + L y 2

Since L x , L y and L z are Hermitian, their eigenvalues must be real.

Eigenvalues of L 2x , L 2y 0 L 2 L 2z 0

l ( l + 1) 2 m l 2 2 0 ml l ( l + 1) - verification of an already known result

( )
When L + L is operated on l ml , l remains constant and ml increases (decreases) by

one unit, but, it can occur up to a certain limit. i.e. there must be some maximum and
minimum values of ml such that L + l mT = 0 L l mB = 0

L + l mT 0
= L L + l mT 0
=

{
(
L2 L z L z + )} l mT 0
= { l ( l + 1) 2
mT ( mT + ) }l mT 0
=

l (l =
+ 1) mT ( mT + 1) mT
= l or ( l + 1)

Similarly, it can be shown that mB =

l or ( l + 1)
Therefore, the allowed values of ml are in the range from l to + l .

Now consider, L +=
l ml C+ l ml + 1 l ml L +
= C+* l ml + 1

l ml L L + l =
2
ml C+ l ml + 1 l ml + 1

l ml L 2 L 2z L z =
2
l ml C+ l ml + 1 l ml + 1
2
l ( l + 1) 2 ml ( ml + 1) 2 l ml l=
ml C+ l ml + 1 l ml + 1

Using the normalization of spherical harmonics,

l ml l ml = l l ml ml and assuming C+ as a real and positive,

C+ = l ( l + 1) ml ( ml + 1) = ( l ml )( l + ml + 1)
 31

Similarly, if L =
l ml C l ml 1 , show that

C = l ( l + 1) ml ( ml 1) = ( l ml )( l ml + 1)

Matrix representation of L z , L2 , L + and L in the basis of { l ml }
L z
= ( ) l ml , l ml
l ml L z l ml
= m ml ml

( )

L2 =
l ml , l ml

l ml L2 l m=
l l ( l + 1) 2 ml ml

L z and L 2 are represented by diagonal matrices.

( L )
+
l ml , l ml
= l ml L + l ml = l ( l + 1) ml ( ml + 1)
12
ml , ml +1

( L )

l ml , l ml
= l ml L l ml = l ( l + 1) ml ( ml 1)
12
ml , ml 1

1 1
L x
Since=
2
(
L + + L ) and
= L y
2i
( )
L + L , from the above results, matrix

representations of L x and L y can be found.

By looking at the expectation values of L 2 , L x , L y and L z in the state l ml

L=
2
l ml L 2 l m=
l l ( l + 1) 2
1
L x = l ml L x l ml = l ml L+ + L l ml = 0
2
1
L y = l ml L y l ml = l ml L+ L l ml = 0
2i
=L z l ml L z l ml
= ml

We know that for a given value of l, ml can take on ( 2 l + 1) number of values ranging from

l to l . From the above results, we see that, the average values of Lx and Ly always vanish

but that of Lz is given by ml . These facts suggest the vector model of L according to which

L precesses about the axis of quantization (z-axis) with ( 2 l + 1) projections of L on this axis

being given by m l , ml = l , ......., + l . L may be viewed as lying on the surface of a cone

with altitude ml which has the z-axis as the axis of symmetry and all the orientations of L
on the surface of the cone being equally likely.
 32

L+

Spin Angular Momentum Operators and Eigenfunctions

Spin angular momentum of electron was postulated by Uhlenbeck and Goudsmit (in 1925)
as a convenient concept to explain the anomalous splittings observed in spectral lines in
Zeeman effect experiment. According to Uhlenbeck and Goudsmit, electrons spin angular
momentum has two orientations relative. to an axis of quantization so that its component on
this axis takes the quantized values 2 .

The quantum numbers corresponding to electrons spin angular momentum, s = 12 .

Particles with,
1 Spin-0 Spin-1
Spin- 2
electrons
pion photon
protons
Fermions kaon
neutrons
Bosons
neutrino

Since the spin does not correspond to any classical motion, spin angular momentum operators
can not be built in the manner used for obtaining the orbital angular momentum operators. So
we construct them to have the same forms as orbital angular momentum operators.

Since S is an angular momentum operator, its Cartesian components S x , S y and S z are

Hermitian operators.

S = S x i + S y j + S z k, S 2 = S x 2 + S y 2 + S z 2

They satisfy the commutation relations

= S x , S y S z ,
i= S y , S z S x ,
i= S z , S x i S y


They may also be written as S S = i S or Si , S j = i Sk
 33

S 2 , S x 2
= S 2 , S z
Also, =
S , S y =
0

We can define S=
S x i S y and S+ and S have the same commutation properties as

L + and L .

Also, we can find simultaneous eigenstates of S 2 and S z corresponding to eigenvalues

s ( s + 1) 2 and ms respectively and are denoted by s ms or s , ms .

For a given kind of particles (i.e. for a given value of s ), there are ( 2 s + 1) number of

allowed values for ms , in the range s ms s , i.e. ms = s, s + 1, ........... s 1, s .

These ( 2s + 1) number of eigenstates s ms form an orthonormal basis satisfying

s ms s ms = m ms
s

Consider the basis containing s ms for some values of s .

1
s =
2
12 ,
ms = 1
2
{ 12 12 , 1
2
1
2 }, 02 elements
s =
1 ms =
1, 0, 1 {1 1 , 1 0 , 1 1 } , 03 elements

Since S 2 s ms= s ( s + 1) 2 s ms and S z s ms = ms s ms , by defining

S=
S x i S y (similar to L ), it can be shown that

S=
s ms ( s ms )( s ms + 1) s ms 1 , s ms s .

Since L corresponds to a physical motion, L and its eigenfunctions can be represented in

( )
terms of and i.e. Yl ml ' s . However, the representation of spin wave functions can be

obtained, not as an analytic function but as matrices. The dimensionality of these matrices
depends on the value of s .
For a given value of s , if the ( 2 s + 1) number of eigenvectors s , ms s ms are used as a

basis, the spin operators S x , S y , S z and S 2 are represented by ( 2 s + 1) ( 2 s + 1) square

matrices and the s , ms are represented by ( 2 s + 1) 1 column vectors.

Eg.:- When s = 1 2s + 1 = 2
2

0 1 0 i 1 0 2 3 2 1 0
=S x =

, Sy =

, Sz = , S
2 1 0 2 i 0 2 0 1 4 0 1
 34
1 0
1 1
The two eigenvectors are then = , =
1 1
,
2 2 0 2
,
2 1
1 1
Eigenvectors 1 1 and 1 1 correspond respectively to eigenvalues and
2
,
2
,
2 2
2 2

3
of S z and 2 of S 2 . i.e. they correspond to spin up ( ) and spin down ( )
4
states.

=
= 1,
=
= 0

Note: Given below are several different notations used to denote spin- 12 eigenfunctions.

1 1 1 1
2 2
+ + , 1 1 1
2
12
, ,
2 2 2 2

Eg.:- When s = 1 2 s + 1 = 3

0 1 0 0 i 0 1 0 0 1 0 0
2 2
S x
= S y
1 0 1, =

Sz 0 0 0 , =
i 0 i , = S 2 0 1 0
2 2 0 0 1 0 0 1
0 1 0 0 i 0

The three eigenvectors are then

1 0 0

=1 1 0, 1 0
= 1 , 1 1
= 0 , corresponding respectively to
0 0 1


eigenvalues + , 0 and of S z and 2 2 of S 2 .
Spin-1 eigenfunctions are denoted by the following notations.
1, 1 1 + 1 = + , 1, 0 1 0 = 0 , 1, 1 1 1 =

Note:
In the matrix notation, the orthonormality relation is s ms = , where is
sm m s s ms sms

the Hermitian adjoint of s ms which is a row vector.

Eg.:- 1
s =
2
1 1 (1 0 ) , 1 1 ( 0 1)
=
, ,
2 2 2 2

By checking the orthonormality

1 0
1 =
1 . 1 1 0)
(1= 1, 1 =
1 . 1 1 (1=
0) 0
,
2 2
,
2 2 0 ,
2 2 2
,
2 1
 35

Eg.:- s =
1 (1 0 0 ) , 1, 0 =
1, 1 = ( 0 1 0 ) , 1, 1 =
( 0 0 1)
Check the orthonormality relation.

Ex: - Show that, when s = 12 .

i
=S x = S y = S z
2 2 2
i
S x = S y =
S z =

2 2 2
=S+ 0
= S 0
= S =
S+

S x , S y and S z can be written as

0 z

0 1 S +
=S x = x , where x

2 1 0
2

0 i 3

=S y = y , where y
2

2 i 0 S + S
3
2
1 0
=S x = x , where z
2 0 1 2

S
0
or S =
2
x , y and z are called Pauli spin matrices.
Note:
2 2 2
Tr
= x Tr=
y Tr
= z 0, det x = det y = det z = 1 , =
x =
y
= z I

Using matrix representations of S x , S y and S z , the commutation relation Si , S j = i Sk ,

where each i, j , k = x, y, z , can be verified.

2 0 1
0 i 0 i 0 1
S x , S y = S x S y S y S x =

= i S z
4 1 0 i 0 i 0 1 0
i
It can be also verified that Si S j = Sk
2
When the particle is in either spin-up or spin down state,

2 3 2
Sx2
= S y2
= Sz2
= S2
and =
4 4

Also, for the spin-up state Sx
= Sy
= Sz
0, = ,
2
 36

for the spin down state Sx = Sy = 0, Sz = ,
2
These facts again confirm the vector model of spin angular momentum.

The wave function of a particle having a spin must depend on a spin variable describing the
spin orientation of the particle, in addition to x, y, z and t. Then, in the wave function

( r , t , ) , the spin variable denotes the z-component of the spin angular momentum

which takes ( 2 s + 1) number of discrete values.

The general wave function of a particle having spin eigenfunction s , ms is,

s

( r , t , ) = ms ( r , t ) s , ms ........................ (1)
ms = s

where ms ( r , t ) is the spin-dependent solution of the TDSE and for a given s, there are

( 2s + 1) number of ms ( r , t ) components.

Eg.: When s =12 ms = 12 , + 12

1 (r , t )
1 0
( r , t, ) = 1 ( r , t ) + 1 ( r , t ) = 2 (as given by (1))
2 0 2 1 1 (r , t )
2

Normalization of requires that = 1 .

s 2

= ( r , t, ) ( r , t, ) dr = ms ( r , t ) d r (2)
m = s
s

Eg.: When s = 1 ,
2

1 (r , t )
* 2
= 12 (r , t ) * 1 (r , t ) dr
2 1 (r , t )
2

2 2

= 1 ( r , t ) + 1 (r , t ) d r (as given by (2))
2 2

2
Assume that =1 . Then, ms ( r , t ) d r gives the probability of finding the

particle at time t in the volume element dr with the z-component of the spin equal to ms
s 2

and ms ( r , t ) d r gives the probability of finding the particle at time t in the volume
ms = s

element dr , independent of its spin orientation.
 37
When a particle is in an eigenstate of S z corresponding to a definite value of ms ( say ms )

( r , t, ) = ms ( r , t ) s ms

Eg: For a particle in ms = + 12 state ( r , t, ) =
+1 (r , t ) 1,+ 1
2 2 2

The general spin state of a particle of spin quantum number s

s
s = ams s ms . (3)
ms = s
s 2
2
As s ms s ms = ms ms , if s s = 1 , then
ms = s
ams = 1 , where ams gives the

probability that the particle in the spin state s being found in the basic spin state s ms on
measurement.
Eg: When s = 1
2
, the general spin- 12 wave function
=1 a1 1 + a 1 1 (using equation (3))
,1 , 1
2 2 2 2 2 2 2
a
= a + b = , where 1 , a a1 , b a
1
b 2 2 2
2 2
If =1 a + b 1.
=
2 2
Here a and b are the probabilities of finding the particle in spin up and spin down (i.e.
in and states) when measuring S z .

Since S 2 s=
ms s ( s + 1) 2 s ms S 2 =
s s ( s + 1) 2 s
s
ms ( r , t ) S 2 s ms = s ( s + 1) 2 ( r , t , )

Equation (1) S 2 ( r , t , ) =
ms = s

If there are no spin-dependent interactions, Hamiltonian will be spin-independent.

( r , t, ) =
( r , t ) s ,

where ( r , t ) is the spinless solution of the TDSE and s is the spin function of the particle.

ams ( r , t ) and there are
From equation (1) and (3), it can be concluded that ms ( r , t ) =
(2s+1) number of such functions.

In the orthonormal basis { , } ( and are simultaneous eigenstates of S 2 and Sz ), it is

possible to find the eigenvalues and corresponding eigenstates of S and S . x y

0 1
Eg: S x =
2 1 0
p
Eigenvalue
= equation, S x X x X , where X
=
q
 38
Eigenvalues x are given by S x x I 0
=
x
2
0
= x =
2

2
x
p
To find the eigenvectors for each value of x ,
q
0 1 p p
x = + 2 = p =
q.
2 1 0 q 2 q
p
By normalizing X , X X 1
= (p *
)
q* =1
q
2 2 1
p + q =1 p ==
q
2
1 1 1 1 1 0 1 1
X= or X + 12 = + +
2 1 2 0 2 1 2 2

1 1 1 1 1 0 1 1
Similarly, when x = 2 , X1 = or X 12 =
2
2 1 2 0 2 1 2 2

{ }
In the basis X + 1 , X 1 , the matrix S x is diagonalised with elements 2 .
2 2

0 i
Repeat the above procedure for S y = .
2 i 0

Addition of Angular Momenta

Consider two angular momenta J1 and J 2 and their corresponding z-components given by
J1z and J 2 z respectively.

J12 j1 m j1 = j1 ( j1 + 1) 2 j1 m j1
J 22 j2 m j2 = j2 ( j2 + 1) 2 j2 m j2

J1z j1 m j1 m j1 j1 m j1
= J 2 z j2 m j2 m j2 j2 m j2
j1 m j1 j1 j2 m j2 j2

It is possible to find normalized simultaneous eigenvectors of J12 , J 22 , J1z , J 2 z , as denoted
by j1 j2 m j1 m j2 and obtained by j1 m j1 j2 m j2 , corresponding to eigenvalues
j1 ( j1 + 1) 2 , j2 ( j2 + 1) 2 , m j1 , m j2 respectively. There are ( 2 j1 + 1)( 2 j2 + 1) number
of j1 m j1 j2 m j2 basis vectors representing different angular momentum states of the
system.

Now consider the total angular momentum J and its z-component J z , as given by

= J J1 + J 2 ,
= J z J1z + J2 z .
 39

j1 j2 m j1 m j2 is an eigenvector of J z corresponding to the eigenvalue m j1 + m j2 . (show ( )

this as an exercise).

J2 j mj = j ( j + 1) 2 j m j , J z j m j = m j j m j , where j m j j

It is also possible to find the normalized simultaneous eigenvectors of J12 , J 22 , J 2 , J z as
denoted by j1 j2 j m j , and the corresponding eigenvalues as j1 ( j1 + 1) 2 ,
j2 ( j2 + 1) 2 , j ( j + 1) 2 and m j respectively.
mj =( m j1 + m j 2 ) mj =m j1 + m j 2

We can therefore describe the angular momentum state of a system in terms of

j1 j2 m j1 m j2 or j1 j2 j m j . We can not use all six quantum numbers simultaneously at
one instant.
If can be shown that the range of j is such that j1 j2 j j1 + j2 (in integer steps)
and for each j value, the range of m j is j m j j (2j + 1 number of values)

Therefore the number of elements in the basis consisting of j1 j2 j m j states

j1 + j2
= ( 2 j + 1) = ( 2 j1 + 1)( 2 j2 + 1)
=j j1 j2

Both representations have the same number of states.

Eg: Let J1 L, J 2 S J =L + S
=l 0, = 1, 2, ....... s 12
For a p-electron, l =1 ml =
1, 0, + 1
s=
1
2
ms =
12 , 12
The possible states of l s ml ms are
1 1
2 1 12 , 1 1
2 0 12 , 1 1
2 1 12 , 1 1
2 1 1
2 , 1 1
2 0 1
2 , 1 1
2 1 1
2

Possible values of j are 1 1

2 j 1+ 1
2 j =12 , 3
2

j =1
2 mj = 12 , 1
2 and j =3
2 mj = 23 , 12 , 1
2 , 3
2

The possible states of l s j m j are

1 1
2
1
2 12 , 1 1
2
1
2
1
2 , 1 1
2
3
2 23 , 1 1
2
3
2 12 , 1 1
2
3
2
1
2 , 1 1
2
3
2
3
2

The total number of possible states in both representations = 6

This is also given by (2 l + 1)(2 s + 1) = 3 2 = 6

Ex: Repeat the above work for s, d and f electrons.

 40
The two basis sets of orthonormal eigenfunctions can be related by a unitary transformation.

j1 j2 j m j = j1 j2 m j1 m j2 j m j j1 j2 m j1 m j2 ,
mj , mj
1 2

where j1 j2 m j1 m j2 = j1 m j1 j2 m j2

The coefficients j1 j2 m j1 m j2 j m j are called Clebsch-Gordan or vector coupling

coefficients. These coefficients
(i) mj
are equal to zero unless = m j1 + m j 2 .
(ii) can be determined by applying raising and lowering operators , J
(iii) have been tabulated for various values of j1 , j2 , m j1 , m j2 , j , m j in Theory of
angular momentum books.

Eg: (i) Addition of spin angular momenta S1 and S2 of two (spin- 12 ) particles.

S
= S1 + S2 , S z
= S1z + S2 z

Q. numbers associated with S1 and S2 are s1 = 12 and s2 = 12 and that with S is S .
Q. numbers associated with S and S are m = 1 and m = 1 and that with
1z 2z s1 2 s2 2
S z is M S .
According to the rules of addition of angular momenta, the allowed values of S are
s1 s2 S s1 + s2 S = 0, 1
M
= S ms1 + ms 2 M S = 1, 0, 1 and 0
(Also, when S =
0 MS =0 and when S=
1 MS =
1, 0, 1 )

The simultaneous eigenfunctions of S12 , S22 , S1z , S2 z can be written as
s1 s2 ms1 ms2 = s1 ms1 s2 ms2

Since the simultaneous eigenfunctions s1 ms1 of S12 and S1z are (1) and (1) ,

and s2 ms2 of S22 and S2 z are (2) and (2) , we construct s1 s2 ms1 ms2 as
(1) (2), (1) (2) (1) (2), (1) (2) .

Then, the simultaneous eigenfunctions of S12 , S22 , S 2 , Sz can be given by
S , M S (1, 2) s1 s2 S M S s1 s2 ms1 ms2 S M S
= s1 s2 ms1 ms2
ms , ms
1 2

1
S=
0 MS =
0 0, 0 (1, 2) = [ (1) (2) (1) (2) ] Singlet spin state
2
Anti-symmetric under the interchange of spin co-ordinates
 41
MS =
1 1, 1(1, 2) = (1) (2)
1
S=
1 MS =
0 1, 0 (1, 2) = [ (1) (2) + (1) (2) ] Triplet spin states
2
MS =
+1 1, +1(1, 2) = (1) (2)
Symmetric under the interchange of spin co-ordinates

The above S , M S are eigenfunctions of S 2 and S z with the eigenvalues S ( S + 1) 2 and
MS .
Eg: The lowest state of the helium atom (which contains two electrons) is a singlet state while
excited states can be either singlet or triplet.

(ii) Addition of spin and orbital angular momenta L and S of a (spin- 12 ) particle.

J= L + S ,
J= z L z + S z

Q. numbers associated with L and S are l = 0, 1, 2, 3, ..... (depending on the

electrons sub shell) and s = 12 and that with J is j . Q. numbers associated with L z
and S are m = l , l + 1, ....., l 1, l and m = 1 and that with J is m .
z l s 2 z j
According to the rules of addition of angular momenta, the allowed values of j are
l 1
2 j l+ 1
2 l 12 when l 0
j = and 1 when l =
j =
2
0
m= ml + ms m= ml 1
j j 2

l s j mj = l s ml m s j m j l s ml ms ,
ml , m
s

and l s ml ms = l ml s ms , where l ml are spherical harmonics and

s ms are single electron spin functions ( and ).
 42
Approximation Methods
In quantum mechanics, approximation methods are used to solve problems when they can not
be solved exactly. Such problems can be divided into two groups according to whether the
Hamiltonian of the system is time-independent or time-dependent. In this section, we first use
approximation methods to determine the discrete eigenenergies and corresponding
eigenfunctions for stationary states of a time-independent Hamiltonian. Here we apply
perturbation theory which studies the change induced in a system by a small perturbation.

Time-independent perturbation theory for a non-degenerate energy level

H
= H 0 + H ,

where H 0 unperturbed Hamiltonian, H perturbation (small) << H 0 and H perturbed

Hamiltonian. 0 1 and determines the order of the perturbation calculation.

H 0 satisfies the TISE, H 0 n( ) = En( ) n( ) and we should know how to solve this and find
0 0 0

En( ) and n( ) . The functions n( ) form a complete orthonormal set, i.e. i( ) (j ) = i j

0 0 0 0 0

If En is the perturbed energy level corresponding to H ,

H n = En n .

We assume that the perturbation is small and that the level En is closer to En( ) than to any
0

other unperturbed level.

En( ) , lim n n( )
0 0
lim En
= =
0 0

Assuming that En and n can be expanded in powers of as

=En
= j En( ) ,j
n j n( j ) ,
=j 0=j 0

where j is the order of perturbation, and substituting them in H n = En n ,

( H 0 )( 1 2
) ( 1 2
)(
+ H n( ) + 1 n( ) + 2 n( ) + ...... = En(0) + 1 En( ) + 2 En( ) + ...... n( ) + 1 n( ) + 2 n( ) + ......
0 0 1 2
)
Equating the coefficients of equal powers of on both sides,

0 H 0 n( 0) = En( 0) n( 0) zeroth order ----------------- (1)

1 H 0 n(1) + H n( 0) = En( 0) n(1) + En(1) n( 0) - first order ----------------- (2)

2 H 0 n( 2) + H n(1) = En( 0) n( 2) + En(1) n(1) + En( 2) n( 0) - second order ------------ (3)

 43

H 0 n( ) + H n( =
j 1)
En( ) n( ) + En( ) n( ) + ........ + En( ) n( )
j 0 j 1 j 1 j 0
j - j th order

To find the energy corrections En( ) , En( ) , ....... etc , multiply each of the above results by
1 2

n( 0) * and integrate over all co-ordinates.

H 0 n( ) En( ) n( ) n( 0) H 0 n( 0) En( ) n( ) n( )
0 0 0 0 0 0
= =

En( ) = n( 0) H 0 n( 0)
0

Similarly, from the 1st order result,

n( 0) H 0 n(1) En( ) n( ) n( )
0 0 1
+ n( 0) H n( 0) En(1) n( 0) n( 0) 0
=

Since H 0 is Hermitian,

n( 0) H 0 n(1) = H 0 n( ) n( )
0 1

* *
= n(1) H 0 n( 0)
= E
=n
( )
0
n( ) n( )
1 0
En( ) n( ) n( )
0 0 1

Therefore, the first-order correction to energy,

En( ) = n( 0) H n( 0)
1

Now the energy of the new state correct to the first-order can be found by using the original
state with H and evaluating the above integral.
Following the above procedure,

En( ) n( 0) H En(1) n(1)

2
=

We need to know n( ) , in order to determine En( ) ,

1 2

En( ) = n( ) H En( ) n( ) 2 En( ) n( ) n( )

3 1 1 1 2 0 1

Eg:- Various order corrections for the nth energy level

En( ) + En( ) + 2 En( ) = En
0 1 2

En( ) + En( ) = En
0 1

En( ) = En
0

After making the first order correction, the energy of the perturbed state must be slightly
deviated from the energy of the original (unperturbed) state and after making the second
order correction, the energy must be deviated even slightly further from the energy obtained
after the first order correction. Depending on the type of the problem, some of these
corrections can be zero.
 44

To find n( ) , we first solve, H 0 n( ) = En( ) n( ) for all En( ) and n( ) and then expand n( )
1 0 0 0 0 0 1

(1) ( 0 )
in the basis of n( ) , n(1) = ank
0
k .
k

Substituting this in the expression (2) obtained for the first order, multiplying by l( ) and
0*

integrating over all co-ordinates,

l( ) H 0 an( k) k( ) (1) (0) (0)

En( ) an k l k
(0) (0)
+ l H n( ) En( ) l n( )
0 1 0 0 0 1 0
0
=
k k

l( ) Ek( ) an( k) k( ) En( 0) anl( ) + H ln En(1) l n =

0 0 1 0 1
0
k

Ek( ) an( k) l( ) k( ) En( 0) an( l) + H ln En(1) l n =

0 1 0 0 1
0
k

El( ) an( l) En( ) an( l) + H l n En( ) l n =

0 1 0 1 1
0

En( ) = H n n En( ) = n( 0) H n( 0)
1 1
For l = n,

For l n, ()
anl
1
= H l' n ( E( ) E( ) )
n
0
l
0

an( n) can not be determined from the above relationship. So, we could write
1

l( ) H n( 0)
0
(1)
l( )
0
n =
( 0)
( 0)
ln En El

To find n( ) use the expansions

2

() ( ) ( ) ( )
n( ) n( 2) ank
1 1 0 2 0
= = ank k , k
k k

and substitute them in the expression (3) obtained for the second order. Then, by following
the same procedure

En( =
2)
H nk ank( ) ()
H nk ank( )
1 1 1
for l = n, ann
H nn =
k kn

2
( 2) H k n
H nk H k n
=En
=
( 0)
( 0)
En( ) Ek( )
0 0
k n En Ek k n

*
n( 0) H k( ) k( ) H n( 0)
0 0
Note: Since H is Hermitian, = = H k *n
H nk

If n corresponds to the ground state of the system, for k n (i.e. k corresponds to an excited

state), En( ) is always negative for any perturbation H .

2
 45

En = En( ) + En( ) + En( ) , ( = 1)

0 1 2

2
H k n
En = En( ) + H nn
0
+
En( ) Ek( )
0 0
k n

For l n ,
1 H lk H k n H ln
H nn H ln
anl( ) (1)
2
= ann
En( ) El( ) En( ) Ek( )
( ) En( ) El( )
0 0 0 0 2 0 0
En( ) El( )
k n 0 0

( )
2
ann can not be determined from this

From other methods, it can be shown that,

() ( ) 1 (1) 2
1
ann = 0, ann =
2

2kn
ank

n( 0) + n(1)
n = ( =
1)

H ln
n(1) = l( )
0
where
( 0) ( 0)
ln En El

2
( 2) H lk H k n H ln
H nn (0) 1 H k n
=n (0) (0) (0) (0)
2 l
n( 0)
(
l n k n E

n El )(
En Ek ) (En( ) El( )
0 0
)
2 k n (0)
En Ek( )
0
( )
2

Notes:
1. The success of this method depends on series converging rapidly.

2. En( ) is easily calculated but unfortunately it is frequently equal to zero due to some
1

symmetry rules.

3. For En( ) to be small, the state n( ) , should not be degenerated

2 0

En( ) Ek( ) En( ) )

0 0 2
(when =

But if k( ) H n( ) = 0 for these degenerate states, En( ) may still be calculated.

0 0 2

4. For the ground state, En( ) 0 .

2
 46
Time-independent perturbation theory for a degenerate energy level
Unlike in the previous case, here we assume that the unperturbed energy level En( ) is -fold
0

degenerate i.e., there are several unperturbed wave functions n( r) ( r = 1, 2, 3, 4, ., )

0

corresponding to this level and we dont know exactly which of these functions the n' s

tend to when 0.

El( ) En( ) , l( ) and nr

( 0)
0 0 0
For are orthogonal. We also assume that,

( 0) ( 0)
=
nr ns =
rs ( r , s 1, 2, ....., )

El( ) l( 0)
0
Eg:- Energy spectrum of hydrogen
n=3

n( 0)

En( ) n( 3) 2P+1
0 0

n=2
n( 2) 2P0
0

2P1
n( 1)
0

n=1 2s
1s
Expand the perturbed wave function nr and energy Enr is powers of .
( 0) (1) ( 2)
nr = nr + 1 nr + 2 nr + ...............

Enr = En( ) + 1 Enr

(1) ( 2)
0
+ 2 Enr + ...............

where n( r) = Cr s n(0s)
0
are called correct zeroth-order function and Cr s are to be
s =1

( )
functions as given by n(1 ) , n( 2) ,
0 0 0
determined. Note that, there is an number of nr

., n( )
0
and there is an number of Cr s coefficients as given by

C11 , C12 , ......., C1 , C21 , C2 2 ,......., C2 , ....., C 1 , C 2 ,....., C

 47

We know how to solve H 0 n( r) = En( ) n( r) and we have to solve H n r = En r n r , where

0 0 0

H
= H 0 + H . Substituting the expansions nr and Enr in H n r = En r n r and equating

the coefficients of ,

H 0 n( r) = En( ) n( r)
0 0 0
0 : This is not a new result as we can get it from the TISE

of the unperturbed system, H 0 n( r) = En( ) n( r) .

0 0 0

(1)
H 0 nr + H n( r) = En( ) n( r) + En( r) n( r) .................. ( A)
0 0 1 1 0
1 :

() 1
Expanding nr in the basis set of unperturbed wave functions and using in expression ( A)

H 0 k( s) ( ) ( )
( s 1, ......... , ) .
0 0 0
with
= E
=k ks

(1)
anr( ), k s k( s) ,
1 0
nr =
k s

an( r), k s ( Ek( ) )

En( ) k( s) + Cr s ( H En( r) ) ns
( )
1 0 0 0 1 0
we get 0
=
=k s 1=s 1

Multiplying on the left by n( u) (u = 1, 2, , ) and integrating over all co-ordinates

0*

an r , k s ( Ek )

(1) ( 0) ( 0) ( 0) ( 0) H n u , n s En(1r) u s =
nu ks + Cr s En
0
k s 1= s 1

where H n u , n s n( 0u) H n( 0s) and u s n( 0u) n( 0s) .

n( u) k( s) Ek( ) En( ) when k

0 0 0 0
Since = 0 when k =
n, = n

Cr s H n u , n s En( r) u s =
1
0 ................. ( B)
s =1

This gives a set of linear homogeneous of equations for the unknown quantities
Cr1 , Cr 2 , ..............., Cr
 48

Cr 1 H n1,n1 En( r) + Cr 2 H n1, n 2 + Cr 3 H n1,n3 + ............... + Cr H n1,n =

1
0

Cr 1 H n 2, n1 + Cr 2 H n 2, n 2 En( r) + Cr 3 H n 2, n 3 + ............... + Cr H n 2,n =

1
0

Cr 1 H n u , n s En( r) + Cr 2 H n1, n 2 + Cr 3 H n1, n 3 + .................. + Cr H n1, n =

1
0

-----------------------
-----------------------
-----------------------

Cr 1 H n , n1 + Cr 2 H n , n 2 + Cr 3 H n , n 3 + ............... + Cr H n , n En( r) =
1
0

Equivalently, the above set of equations can be written in the matrix form as

(
H
n1, n 1
En( r)
1
) H n 1, n 2 H n 1, n 3 - - - - - - - - - - - H n 1, n
Cr 1
C
H n 2 , n1

(
H n 2 , n 2 En( r)
1
) H n 2 , n 3 - - - - - - - - - - - H n 2 , n r2
-


- - - - = 0
- - - - -
-
H
n , n1 H n , n 2 (
H n , n 3 - - - - - - - - - - H n , n
1
)
En( r) C
r

For a non trivial solution of the above matrix equation, it is required that

det H n u , n s En( r) u s
1
0 . (C)
=

(H n 1, n 1 En( r)
1
) H n1, n 2 H n1, n 3 - - - - - - - - - - - H n1, n

H n 2 , n 1 (H
n 2,n 2 En( r)
1
) H n 2 , n 3 - - - - - - - - - - - H n 2 , n
- - - - = 0
- - - -
H n , n 1 H n , n 2 (
H n , n 3 - - - - - - - - - - H n , n En( r)
1
)

This is an equation of degree in En( r) , r = 1, 2, ............ , . The possible number of

1

roots are En( 1) , En( 2) , .............. , En( ) .

1 1 1
 49
If the above roots are all distinct, the degeneracy exhibited in the nth energy level is
completely removed, if they are all equal, the degeneracy is preserved and if some of them
are equal, the degeneracy is only partly removed, in the first order of level n.

For each value of ( r = 1, 2, ......, ), the coefficients Cr s ( s = 1, 2, ......, ) can be

determined by substituting En( r) in (B) and solving for Cr 1 , Cr 2 , ..............., Cr . Then the
1

correct zero-order wave functions n( r) can be determined.

0

Note: In the basis consisting of unperturbed wave functions n( r) , if all the off-dioganal { } 0

(
elements of the matrix representing H i.e. H n u , n s n( 0u) H n( 0s) with r s )
En( r) n( 0r) H n( 0r)
1
vanish, then equation (C) gives
= H
= n r , n r ( r = 1, 2, ......, )

which are diagonal elements of H matrix.

The above result shows that, if the above condition is satisfied, the degeneracy plays
no role in the analysis and the degenerate level can be treated in the same manner
used for a non-degenerate level. This situation occurs when the unperturbed states can
be uniquely specified in terms of a set of operators which all commute with H . i.e.
A , H
= 0, B , H
= 0 and the set of unperturbed wave functions can be

{ }
given as a( b) , where a and b are quantum numbers associated with A and B .
0

If the above situation does not occur and therefore the matrix of H in the basis of

n( 0r) is not diagonal, one could form proper orthonormal linear combinations of n( 0r)

as n r = Cr s n( s) and choose suitable values for Cr s so that the matrix of H in
( 0) 0

s =1

the basis
= { }
n( r) is diagonal. i.e. H n r , n s
0
( n( 0r) H n( 0s) should vanish when r s . )
En( r) n( 0r) H n(0)r ,
1
=
Then, H n r , n r
= (r = 1, 2, ......, )
 50
Applications of Perturbation Theory
(1) Stark Effect of one-electron atoms
Stark effect is the splitting occurred in energy levels when atoms are subjected to external

static electric fields. When a charge q is placed in an electric field of strength E , the

associated potential energy = q. E. r
For an electron of charge e placed in an electric field applied along the z-direction, the
potential energy = eE z

2 2 Z e2
Hamiltonian of the unperturbed atom, =H 0
2 ( 4 0 ) r
Perturbation H = e E z

2 2 Z e2
Hamiltonian of the perturbed atom, H = + eE z
2 ( 4 0 ) r

Solutions to the TISE H nl ml (r ) = En nl ml (r ) , with the Hamiltonian H 0 have already

been obtained. Hydrogenic atom wave functions nl ml ( r ) n(0) and hydrogenic energies

En En(0) .
The ground state of a one-electron atom is non-degenerate.

EG(1)
= G(0) H G(0)
= eE 100 z 100 *
= e E 100 cos 100 (r )d 3 r
(r ) r = 0

i.e. for the ground state, there is no energy shift that is linear in E.

Classically, a system with electric dipole moment d in an electric field of strength E will
experience an energy shift of d .E . Thus, the atom in its ground state can not have a
permanent dipole moment.

Using the expression that gives the 2nd order correction

2
k(0) H n(0)
En(2) = En(0) Ek(0)
k n

2 2
nl(0)m e E z 100
(0)
nl(0)m z 100
(0)

EG(2) e2 E 2
l l
= =
n l ml E1 En n l ml E1 En
n 1 n 1

Since E1 En ( n 2 ) is always negative, EG(2) < 0

 51
Ground state energy is lowered by the quadratic Stark effect.

Since the above summation can not be evaluated exactly, to obtain a lower limit, we replace
( E1 En ) by ( E1 E2 )
2
nl m l z 10 0 1 2
EG(2) = e2 E 2 > e2 E 2 nlm l z 100
n 1 En E1 E2 E1 n 1
l , ml l, ml

2 2
n l ml z 100 = n l ml z 100 ( Since 100 z 100 = 0 )
n 1 n , l , ml
l , ml

= 100 z n l ml n l ml z 100
n , l , ml

Since nlml from a complete set, n l ml n l ml =1

n l ml

100 z n l ml =
n l ml z 100 100 z 2 100
= z2
100
n , l , ml

1 2 a0 2
But, z2
= x2
= y2
= r
=
100 100 100 3 100 Z2
8 a03 2
EG(2) > ( 0) 4 E
4
3 Z
From other theoretical treatments, an exact value of EG(2) can be obtained as

a03 41 E
2
EG(2) = 2.25(4 0 ) E 2
= 3.71 10
Z4 J
Z4

EG(2) 0.02 cm 1 =0.02 1.2398 104 eV for atomic hydrogen, for a field strength

E = 108 V m 1
2
n l ml z 100
By differentiating EG(2) = e2 E 2 with respect to E, we get the magnitude
E1 En
2
EG(2) n l ml z 100
of the electric dipole moment, D =
E , where = 2 e2
= .
E n 1 En E1
l , ml

( is called as the dipole polarisability of the atom in the ground state)

1
With the above definition of , EG(2) = E2
2
 52
Ex: Calculate the first order (linear in E ) Stark effect for the n = 2 level of hydrogen.
Hint: Consider the fact that the four n = 2 states 200 , 210 , 211 and 211 have the
same energy. i.e. the n = 2 level is 4-fold degenerate. (Ref: Pages 528 - 530,
Introduction to Q.M. by B & J.)

(2)Correction to energy levels of one-electron atoms obtained from Schrodinger

theory, due to relativistic effects Fine structure of atomic energy levels

p4
(i) Relativistic correction to kinetic energy - Perturbation H 1 = (show this)
8 me3 c 2
1 1 dV (r )
(ii) Spin-orbit interaction- Perturbation H 2 = ( r ) L . S where ( r ) = and
2 me2 c 2 r d r
Z e2
V (r ) = .
( 4 0 ) r
2 Z e2
(iii) Relativistic correction to potential energy- Perturbation H 3 = ( r )
2 me c 2 4 0
(Darwin term, acts only at the origin)
p 2 p 2 Z e2
Unperturbed Hamiltonian H0 = + V (r ) =
2 me 2 me ( 4 0 ) r
( = me for heavy nuclei)
Perturbed Hamiltonian H
= H 0 + H , where H = H 1 + H 2 + H 3

(0) (0) (0)

From earlier work, we have H 0 nl ml ( r ) = En nl ml ( r )

nl(0)m (r ) - hydrogenic energy eigenfunctions,
l
2
me Z e 2 1
En(0) =
2 , n =
1, 2, 3, ........... - hydrogenic energy eigenvalues
2 4 0 n 2
Taking electron spin into account

nl(0)m sm = nl(0)m (r ) s ms , ms = 12
l s l
(0)
Wave functions nl m sm
satisfy the TISE with H 0 , H 0 nl
(0) (0) (0)
m sm = En nl m sm
l s l s l s

(0)
It can be shown that nl m sm
are simultaneous eigenfunction of H 0 , L2 , L z , S 2 , S z with the
l s

eigenvalues En(0) , l ( l + 1) 2
, ml , s ( s + 1) 2 and ms (Show this). Since there are 2n 2
(0)
number of nl ml sms
eigenfunctions for each energy level En(0) , degenerate perturbation theory
should be used. (Once n is specified, the degeneracy of the level is determined by
l , ml , s and ms values). It can be shown that, with the perturbation H1 all the operators

L2 , L z , S 2 and S z commute and the previously constructed set of unperturbed wave
(0)
functions nl m sm
have been uniquely specified in terms of the quantum numbers associated
l s

with them.
 53
(0)
Therefore, the matrix of H1 in the basis of nl m sm l s ( i.e. nl(0)m s m H 1 nl( )m s m
l s
0
l s ) becomes
diagonal and the first order corrections to energy due to H1 are given by the diagonal
elements.
(1) p 4
nl m sm H nl( m) sm
( 0) ( 0)
nl( m) sm
0 0

= E1 = nl m sm
l s l s l s
8me3 c 2 l s

1 p 2
= (0) 2
nl m sm T nl m sm ,(0)
T = = H 0 V ( r )
2me c 2 l s l s
2 me
1
= 2
nl(0)m T 2 nl(0)m , Since T does not act on sms
2me c l l

1 Ze 2 Ze 2 (0)
=
nl(0)m
H 0 + H 0 +
2me c 2 l
( 4 0 ) r
( 4 0 ) r nl ml
2
( )
1 ( 0) 2
( 0) Ze 2 1 Ze2 1
=
En + 2 En +
2me c 2 ( 4 0 ) r ( 4 ) r2
nlml 0 nlml

2
1 me c ( Z )
2
1 Z2 1 Z2 ( 0)
Since = , = , En =
r n l ml a0 n 2 r2 nl ml a02 n3 ( l + 12 ) 2 n2
2
(1) ( 0 ) ( Z ) 3
n e2 1
E1 En
= , =
n 2 4 l + 12 4 0 c 137

In the case of the perturbation H 2 = ( r ) L . S , the previously used set of zeroth-order wave
( 0)
functions nl m sm does not make the matrix of H 2
l s ( i.e. nl(0)m s m H 2 nl( )m s m
l s
0
l s ) diagonal
Therefore, linear combinations of nl(0)ml s ms have to be formed (as correct zeroth-order wave
functions) so that they make the matrix of H 2 diagonal. For this, consider,

J = L +

S

L.S =
1
2 (
J 2 L2 S 2 )

When l , s and j are the associated quantum numbers of L , S and J , we have
ls j l+s j = l 1
2 for l 0 and j = 1
2 for l = 0

For a given value of j, j m j j m j = j , j + 1, ........, j . Now

( 0)
consider the new set of unperturbed wave functions nl s j m which are simultaneous
j
2
eigenfunctions of L2 , S2, J and J z with eigenvalues l ( l + 1) 2 , s ( s + 1) 2 , j ( j + 1) 2
and m j respectively.

Then, from our knowledge on addition of angular momenta

nl( s) j m = ( 0)
0
l ml s ms j m j n l m s m
j l s
ml , ms
 54

It can be shown that L. S=
1
2 (
)
J 2 L2 S 2 commutes with L2 , S 2 , J 2 and J z .

H 2 commutes with L2 , S 2 , J 2 and J z .

Therefore, ( 0 ) nl s j m j form a basis in which the matrix of H 2 i.e. n(0)l s j m j H 2 (0)
n l s j m j

is diagonal.

The first-order corrections, E2(1) due to H 2 are given by the diagonal elements of the
above matrix.
1
nl( s) j m ( r ) J 2 L2 S 2 nl( s) j m
0 0
i.e.
= E2(1)
j
2

j

2 3
nl( s) j m ( r ) nl( s) j m j ( j + 1) l ( l + 1)
0 0
=
2 j j
4

2 3
= (r ) j ( j + 1) l ( l + 1) 4
2 nl s j m j

2 1 Ze 2 1 3
= 3 j ( j + 1) l ( l + 1) 4
2 2 me 2 c 2 4 0 r n ls jmj

Z j ( j + 1) l ( l + 1)
3 3
2 1 Ze2 4
=
2 2 me 2 c 2 4 0 a03 n3l ( l + 12 ) ( l + 1)

4
me c 2 ( Z ) l j = l + 12
= when l 0
4n3l ( l + 12 ) ( l + 1) l 1 j = l 12

0 E2( ) =
1
When l = 0 (i.e. for s-states), L.S = 0

H 3 term does not act on the spin part of the wave function and it commutes with L2 and L z .
(0)
In this case, the original set of zeroth-order wave functions nl m sm
makes the matrix H 3
l s

diagonal. Since H 3 acts only at the origin and the hydrogenic wave functions vanish at r = 0

when l 0 , we have only to consider the case l = 0.

2 Ze2 (0)
E3(1) = n l ml sms ( r ) n l ml sms
(0)
2 2

2 me c 4 0

2 Ze2 (0)
= ( r ) ( r ) (0)
( r )
2me 2 c 2 4 0
nl ml nl ml
 55

2 Ze2 (0) (0)

= 2 2
n 0 0 ( r ) ( r ) n 0 0 ( r )
2 me c 4 0
2
2 Ze2 (0) 1 2 ( Z ) ( Z )2
n 0 0 ( 0 ) n 0 0 ( 0 ) = me c
(0)
= 2 2

2me c 4 0 2 n2 n
2
(0) Z ( )
En
= , l=
0
n
2
(1) 1 ( Z ) ( Z )2 n 3
E E1(1)
= + E2(1) + E3(1) me c 2
=
2 n2 n 2
j+2
1 4

( Z )2 n 3
=En(1)j En(0) for all l
n2 j+2
1 4

2
( Z ) n 3
En j = En(0) + En(1)j = En(0) 1 +
n2 1
j+2 4

For a given value of n, there are n number of values possible for j as 1 3 5
, , , .......,
2 2 2
n 12 .

Binding energy En j of the electron is slightly increased with respect to the non-relativistic

value En(0) . En j decreases as n and j increase.

The degeneracy of the unperturbed (non-relativistic) level En(0) is 2n 2 .

When the relativistic effects are taken into account, according to the value of j, the energy
level is split into n number of fine-structure components. i.e. the degeneracy is partially
removed. Fine-structure components of sublevels nl are characterized by the spectroscopic
notation nl j .

Eg: Consider the splitting of n = 1 and n = 2 energy levels in atomic hydrogen.

n=2 2p3 2 2p3 2

2s, 2p

2s1 2

2s1 2 , 2p1 2
2p1 2

1s1 2
n=1
1s
1s1 2
 56
Schrodinger Relativistic Lamb
theory effects shift
As it can be seen from the expression of En j , the levels 2s1 2 and 2p1 2 should have the same

energy (since n and j are the same but l is different). However, this degeneracy is removed
due to small quantum electrodynamical effects, responsible for additional energy shifts called
Lamb shifts.
The transitions n1 l1 j1 n2 l2 j2 between the fine-structure components of the levels n1 l1

and n2 l2 occur under the dipole selection rules

n1 n2 =n arbtrary, l1 l2 =l = 1, j1 j2 =j =0, 1

Identical Particles and Indistinguishability

Two particles are said to be identical if they can not be distinguished by means of any
intrinsic property such as mass, charge and spin. In classical mechanics, identical particles
can be distinguished by their paths and hence cause no problems, but in quantum mechanics,
paths are not well-defined and hence the identity of particles may not be an observable.

V ( x)

A A ( x) B B ( x)

x
0
Consider two identical particles in two infinite potential wells A and B. Since the two
particles have been restricted to their regions we still have no difficulty in identifying them.
But in the case of two finite potential wells, there is a tendency for the particle wave
functions to overlap with each other, i.e., there will be a certain probability of observing
particle A in well B and particle B in well A due to tunneling. This makes it impossible in
quantum mechanics to distinguish between identical particles in regions of space where they
can be found simultaneously.
V ( x)

A B
B ( x) A ( x)

x
0
 57
Identity:
In q. m., two particles are said to be identical, if their Hamiltonian is unchanged under the
interchange of particle co-ordinate labels. i.e. H (1, 2 ) = H ( 2, 1)

Eg 1: Consider a two-electron system

e2 2 2 2 2 e2
r2 H (1, 2 ) = r1 r2 +
2 me 2 me 4 0 r1 r2
r1 e1

e1
r2 2 2 2 2 e2
H ( 2,1) = r1 r2 + = H (1, 2 )
e2 2 me 2 me 4 0 r2 r1
r1
Eg 2: Consider a Hydrogen atom
p
r2 2 2 2 e2
H (1, 2 ) = r1 2r2
e 2me 2M p 4 0 r1 r2
r 1

e
2 2 2 e2
r2 H ( 2,1) =
2M p
2r1
2me
r2 H (1, 2 ) ,
4 0 r2 r1
( M p me )
p
r1

Consider a system of two identical particles and let q i (i = 1, 2) denote the spatial co-
ordinate (continuous) and spin co-ordinate (discrete) of particle i. Since particles are
identical, all the observables corresponding to this system must be symmetric functions of the
dynamical variables. The Hamiltonian H of the system must be symmetric in the interchange
of particles 1 and 2. i.e. H (1, 2 ) = H ( 2, 1)

12 which interchanges the

Now introduce the particle interchange (exchange) operator

variables q1 and q2 so that

12 ( q1 , q2 ) =
( q2 , q1 ) ,

where ( q1 , q2 ) is the associated wave function of H and

12 .

12 is a Hermitian operator.
Ex: Show that,

Pf: Consider two arbitrary functions, ( q1 , q2 ) and ( q1 , q2 ) .

( q1 , q2 ) ( 12 ( q1 , q2 ) ) d1d 2 ( q1 , q2 ) ( q2 , q1 ) d1d 2 ............ (1)

* *
=

( 12 ( q1 , q2 ) ) ( q1 , q2 ) d1d 2
*
( q2 , q1 ) ( q1 , q2 ) d1d 2 ............ (2)
*
=

Since 1 and 2 are dummy indices, by interchanging 1 and 2 on the r.h.s. of equn (2),
 58

( 12 ( q1 , q2 ) ) ( q1 , q2 ) d1d 2
*
( q1 , q2 ) ( q2 , q1 ) d 2 d1 ............ (3)
*
=

Since the r.h.s. of equns (1) and (3) are the same,

( q1 , q2 ) ( 12 ( q1 , q2 ) ) d1d 2 ( 12 ( q1 , q2 ) ) ( q1 , q2 ) d1d 2
* *
=

12 is a Hermitian operator.

Ex: Show that, if H (1, 2 ) = H ( 2, 1) , then

12 , H =
0
Pf: Energy eigenvalue equation of the two-article system reads
H (1, 2 ) ( q1 , q2 ) = E ( q1 , q2 ) ................(1)

Since the labeling doesnt matter, by interchanging 1 and 2,

H ( 2, 1) ( q2 , q1 ) = E ( q2 , q1 ) ................(2)
Since H (1, 2 ) = H ( 2, 1) , for the two-particle system
H (1, 2 ) ( q2 , q1 ) = E ( q2 , q1 ) ...............(3)
By the definition of 12 , ( q2 , q1 ) ............(4)
12 ( q1 , q2 ) =
Operating H (1, 2 ) on equation (4)
H (1, 2 ) H (1, 2 ) ( q2 , q1 )
12 ( q1 , q2 ) =
= E ( q2 , q1 ) (from Eq. (3))
= 12 ( q1 , q2 )
E (from Eq (4))
12 E ( q1 , q2 )
=
12 H (1, 2 ) ( q1 , q2 )
= (from Eq. (1))
H (1, 2)
12 = 12 H (1, 2)
0
12 , H =


0 12 and H .
12 , H = It is possible to find simultaneous eigenfunctions of
12 is a constant of the motion
Note: Like the parity operator,

2
12
Ex: Show that =I , where I is the unit operator.
Pf: 12 ( q1 , q2 ) =
( q2 , q1 )

12 ( q1 , q2 ) =
12
12 ( q2 , q1 )
2
12
( q1 , q2 ) =
( q1 , q2 )
2
12
I ( q1 , q2 )
( q1 , q2 ) = 2
12
=I

12 .
Ex: Find the eigenvalues of

Pf: 12 ( q1 , q2 ) =
( q1 , q2 )
 59
12 ( q1 , q2 ) =
12
12 ( q1 , q2 )

I ( q1 , q2 ) = 2 ( q1 , q2 )

( q1 , q2 ) = 2 ( q1 , q2 ) = 1

When = 1 ,

( q2 , q1 ) = ( q1 , q2 ) Wave functions corresponding to = 1 are said to be

12 .
symmetric under the operation of

When = 1 ,

( q2 , q1 ) = ( q1 , q2 ) Wave functions corresponding to = 1 are said to be

12 .
anti-symmetric under the operation of

In general, S ( q1 , q2 ) and A ( q1 , q2 ) are used to denote symmetric and anti-symmetric

wave functions.

Eg: ( r1 , r2 ) e ( r1 + r2 ) symmetric wavefunction

S=

( r1 , r2 )
= e r1 + r2 not symmetric or anti-symmetric wavefunction

In nature, all particles with 1

2
-odd integer spins ( s = 12 , 32 , 52 , . . . . .) are found to have anti-

symmetric wave functions. These particles are called fermions and they obey Fermi-Dirac
statistics.
Eg: e, , , p, n


leptons baryons

All particles with zero or integer spins ( s = 0, 1, 2, ...) are found to have symmetric wave

functions. These particles are called bosons and they obey Bose-Einstein statistics.
Eg: , k mesons , mesons, w, z , photon

=s 0=s 1

If a system is composed of different kinds of particles (say bosons and fermions), then the
corresponding wave function must be separately totally symmetric or totally anti-symmetric
with respect to interchanges of each kind of identical particles.
Eg: H 2 molecule
The total wave function must be anti-symmetric under the interchange of the (space
and spin) co-ordinates of the two electrons and also anti-symmetric under the
interchange of the (space and spin) co-ordinates of the two protons.
 60
Ex: Symmetric and anti-symmetric states are degenerate in energy.
Pf: H (1, 2 ) ( q1 , q2 ) = E ( q1 , q2 )

12 H (1, 2 ) ( q1 , q2 ) =
12 ( q1 , q2 ) =
E E ( q2 , q1 )

Since H ,
12 =
0

H E ( q2 , q1 )
12 ( q1 , q2 ) =

H (1, 2 ) ( q2 , q1 ) = E ( q2 , q1 )

We have proven that ( q1 , q2 ) and ( q2 , q1 ) are degenerate in energy. But, they may not

possess a particular symmetry (symmetric or anti-symmetric). Then, it is possible to construct

totally symmetric or anti-symmetric wave functions, starting with unsymmetrized wave
functions (i.e. they do not possess symmetry properties under the interchange of qi )

( q1 , q2 ) and ( q2 , q1 ) as follows.
A symmetric wave function constructed as
1
S ( q1 , q2 ) = ( q1 , q2 ) + ( q2 , q1 ) =
S ( q2 , q1 )
2
can be used to describe a system of two identical bosons and an anti-symmetric wave
function constructed as
1
A ( q1 , q2 ) = ( q1 , q2 ) ( q2 , q1 ) = A ( q2 , q1 )
2
can be used to describe a system of two identical fermions. Since S and A are formed as

linear combinations of ( q1 , q2 ) and ( q2 , q1 ) , their eigenvalue must also be E.

The above result can be extended for the case of three or more identical particles.

Consider a system two identical particles for which the Hamiltonian H is the sum of single-
particle Hamiltonians hi (=
i 1, 2 ) , H= h1 + h2 . If u ( q1 ) and u ( q2 ) are the normalized

eigenfunctions of h1 and h2 corresponding to the eigenvalues E and E . ( and are the

characteristic quantum numbers)

Then, a solution of the Schrodinger equation H ( q1 , q2 ) = E ( q1 , q2 ) can be given by

( q1 , q2 ) = u (q1 ). u (q2 ) with E E + E .

= Also, it can be shown that

H ( q2 , q1 ) = E ( q2 , q1 ) where ( q2 , q1 ) = u (q2 ) u (q1 ) and =

E E + E .
 61
In general, ( q1 , q2 ) may not have a particular symmetry with respect to the interchange of

q1 and q2 . However, as shown above, we can construct the total symmetric or anti-
symmetric wave functions as required to describe the two-particle system.
1
Then, S= ( q1 , q2 ) + ( q2 , q1 ) , corresponding to E= E + E
2
1
A = ( q1 , q2 ) ( q2 , q1 ) , corresponding to E = E + E
2
Suppose the two particles are in the same state, i.e.
A ( q1 , q2 ) =0, S ( q1 , q2 ) 0

Therefore, if there are two identical particles in the same quantum state, we can not construct
an anti-symmetric wave function, however, we can construct a symmetric wave function. i.e.
no two identical fermions can occupy the same quantum state but two bosons can.
Only one fermion can occupy a given individual quantum state is known as the Pauli
exclusion principle.

Two-particle systems
For a two-particle system, the wave function is a function of position co-ordinates of each

particle and time (by ignoring the particle spin) (r1 , r2 , t ) , which is a solution to the TDSE

2 2 2 2
with the Hamiltonian H = r1 r2 + V (r1 , r2 , t ) . The function (r1 , r2 , t ) must
2m1 2m2

2
be normalized as (r1 , r2 , t ) d r1d r2 =
1 . When the potential is time-independent, the

(r1 , r2 )ei Et , where
variables in the above solution can be separated as (r1 , r2 , t ) =

2 2 2 2
(r1 , r2 ) is a solution to the TISE, r1 r2 + V (r1 , r2 ) (r1 , r2 ) =E (r1 , r2 ) .
2m1 2m2

Two-electron atoms
A two-electron atom (or ion) consists of a nucleus of mass M and charge + Ze and two
electrons, each of mass me and charge e ( M me ) , that circle around the nucleus.

Eg:
= H ( Z 1),
= He ( Z 2),= Be 2+ ( Z 4) ............
Li + ( Z 3),=

Let r1 and r2 be the position vectors of the two electrons with respect to the nucleus. (origin
of the coordinate system)
 62

1 r12
e 2
e

r1

r2

nuclear mass, M
nuclear charge, +Ze

Taking only the Coulomb interaction between particles into account, (Since M me ,

me ), the Hamiltonian can be written as

2 2 2 2 Ze 2 Ze 2 e2
H = r1 r2 + , r12 = r1 r2
2me 2me ( 4 0 ) r1 ( 4 0 ) r2 ( 4 0 ) r12

We have to solve the Schrodinger equation H ( q1 , q2 ) = E ( q1 , q2 ) , which is not easy.

qi Spin and position variables of the ith electron (i = 1, 2)

If S= S1 + S2 and L= L1 + L2 are the total spin and orbital angular momentum operators, it is

possible to obtain simultaneous eigenfunctions ( q1 , q2 ) of H , L2 , Lz , S 2 , S z , as products

of spatial eigenfunctions ( r1 , r2 ) and two electron spin functions (1, 2 ) . Corresponding to

( q1 , q2 ) , the eigenvalues of L2 , Lz , S 2 and S z are L ( L + 1) 2 , M L , S ( S + 1) 2 and

M S respectively.

Here ( r1 , r2 ) are the solutions of the TISE,

H ( r1 , r2 ) = E ( r1 , r2 )

2 2 2 2 Ze 2 Ze 2 e2
r1 r2 + (r1 , r2 ) =E (r1 , r2 )
2me 2me ( 4 0 ) r1 ( 4 0 ) r2 ( 4 0 ) r12

This equation is unchanged under the interchange of r1 and r2 .

both (r1 , r2 ) and (r2 , r1 ) satisfy the same Schrdinger equation with

the same energy.

Lets denote the space symmetric and space anti-symmetric wave functions of the two-

electron system by + L, M L ( r1 , r2 ) and L, M L ( r1 , r2 ) respectively.

They should satisfy,

 63

+ L, M L ( r1 , r2 ) = + L, M L ( r2 , r1 ) .. space symmetric, called para states

L, M L ( r1 , r2 ) = L, M L ( r2 , r1 ) ..space anti-symmetric, called ortho states

L, M L ( r1 , r2 ) and the corresponding energies can be determined by solving the above TISE.

S , M S (1, 2 ) are the eigenfunctions of S 2 and S z , which we have already constructed so that

=
0 0 (S M S 0) describes
0,= the singlet spin state and 1,1 , 1, 0 , 1, 1

(S =
1, M S =
+ 1, 0, 1) describe the triplet spin states. These singlet and triplet functions are
anti-symmetric and symmetric under the interchange of spin co-ordinates of the two
electrons.

In order to obtain the full wave function ( q1 , q2 ) we have to use the fact that electrons are

fermions and they have to be represented by anti-symmetric wave functions in the

interchange of q1 and q2 (as required by the Pauli exclusion principle). This is done by
taking the product of spin and spatial eigenfunctions so that,
1
( q1 , q2 ) = L+M L (r1 , r2 ) [ (1) (2) (1) (2)] Para wave function (spin singlet)
2
(1) (2)

1
( q1 , q2 ) = LM L (r1 , r2 ) [ (1) (2) + (1) (2)] Ortho wave function (spin triplet)
2
(1) (2)

Now, consider the TISE H ( r1 , r2 ) = E ( r1 , r2 ) . This equation can not be solved exactly
e2
because of the presence of the term in H . So, we use perturbation method to
( 4 0 ) r12
e2
obtain zeroth order expressions for ( r1 , r2 ) and E, by treating as a perturbation.
( 4 0 ) r12
2 2 2 2 Ze 2 Ze 2 e2
H = r1 r2 + = H 0 + H ( H 0 H )
2me 2me ( 0 ) 1 ( 0 ) 2 ( 0 ) 12
4 r 4 r 4 r
H 0 can be written as the sum of two Hamiltonians for one-electron atoms. This model is
called the independent particle model.

2 2 Ze 2
H= h1 + h2 , where hi = r , i = 1, 2
0
2 me i ( 4 0 ) ri

The normalized wave function ni li ml ( ri ) and the corresponding energies Eni have been
i

obtained from one-electron atom Schrodinger equations.

 64

hi ni li ml ( ri ) = Eni ni li ml ( ri ) i = 1, 2
i i

We see that n1 l1 ml ( r1 ) and n2 l2 ml ( r2 ) correspond to energies En1 and En2 and each of the
1 2

products n1 l1 ml ( r1 ) n2 l2 ml ( r2 ) and n1 l1 ml ( r2 ) n2 l2 ml ( r1 ) , is an eigenfunction of H 0
1 2 1 2

corresponding to the energy En1 + En2 . This degeneracy which occurs under exchange of

electron labels is called the exchange degeneracy. It is removed when the 1 r12 term is taken
into account.
We can form their linear combinations to obtain proper space symmetric (+) and space anti-
symmetric () zeroth order wave functions
1
( ) ( r1 , r2 )
0
= n1 l1 ml ( r1 ) n2 l2 ml ( r2 ) n1 l1 ml ( r2 ) n2 l2 ml ( r1 ) ,
2 1 2 1 2

which are also degenerate eigenfunctions of H 0 with corresponding zeroth order energy,

( 0) Z 2e2 1 1 4 0 2
En n =En1 + En2 =
2 + 2 , a0 = 2 .
1 2
( 4 0 ) 2a0 n1 n2 me e

When each electron is in its lowest energy state (i.e. 1s state, for which n 1 = n 2 = 1, l 1 = l 2 = 0,
( 0)
m=
l1 m=
l2 0 ) , En n takes its minimum value.
1 2

Zeroth order value of the ground state energy

( 0)
EG En n( ) ( 0)
1 2
min
=

Z 2 e2 1 1
2 + 2 =
( 4 0 ) 2a0 1 1

Z 2 e2
( 4 0 ) a0
2 Z 2 13.6 eV
=

( e2 ( 4 0 ) 2 a0 = 13.6 eV = ionization potential of a H atom)

( 0 ) ( r1 , r2 ) 0 i.e. the ortho state can not exist

Therefore, the zeroth-order (normalized) ground state wave function

G( ) =
( 0)
0
= + ( r1 , r2 ) 100 ( r1 ) 100 ( r2 ) 1s ( r1 ) 1s ( r2 )
32 32
1 Z Z r1 a0 1 Z
= e 12 e Z r2 a0
1 2 a0 a0
3
1 Z
= e Z ( r1 + r2 ) a0
a0

In the zeroth order, the ground state is non-degenerate. Using G( ) , the 1st order correction to
0

the ground state energy can be given as

(1) e2
G H G( )
( 0) ( 0) * ( 0)
0
=EG = G ( 4 0 ) r12 G d r1d r2
 65
1 1
= = , r1 (=
r1 , 1 , 1 ) , r2 ( r2 , 2 , 2 )
( )
r12 12
r12 2r1r2 cos + r22

Here cos = cos 1 cos 2 + sin1 sin 2 cos (1 2 ) and is the angle between r1 and r2 .
Using the knowledge on Legendre polynomials, it can be shown that
l
1 l
4 ( r< )
r12
= Yl*m (1 , 1 ) Yl ml ( 2 , 2 ) ,
2l + 1 (r> )l +1 l
l = 0 ml = l

where r< and r> are the smaller and larger of r1 and r2 . (Y
00 =1 4 )
l
e2 l
( 4 )2
2 (r )
EG(1)
4 0 l = 0 ml = l =
2
r1 d r1
2l + 1 r 0=
r2 2 d r2
G(0) ( r1 , r2 ) < l +1
(r> )
1 r2 0

Yl m (1 , 1 ) Y0 0 d1 Y00Yl m (2 , 2 ) d2
*
l l
2 l
e2 l
( 4 )
2 ( r< )
EG(1)
4 0
l + 1 r 0= r12 dr1 r22 dr2 G(0) ( r1 , r2 )
(r> )l +1
l 0 ml 0
l = 0 ml = l 2
= 1 r2 0

l 0 0 only when l = 0 , ml 0 0 only when ml = 0

e2 2 1
EG(1)
= 16 2
r1 d r1 2
r22 d r2
G(0) ( r1 , r2 )
4 0 =r 0= r2 0
r>
1
6
e2 1 Z 2
2 Z ( r1 + r2 ) 1
EG(1) = 16 2
r1 d r1 r2 2 d r2 exp
4 0 2 a0 r 0=
= r2 0 a 0 r>
1
6 1 r1
(1) 16e 2 Z 2 2 Zr1 2 2 Zr2 2 Zr2
EG = r1 exp
4 0 a0 r 0 = a0

d r1 r2 exp
r1 r 0= a0
d r2 + r2 exp
a0
d r2

= 1 2 r2 r1
5 e2
EG(1)
= Z
8 ( 4 0 ) a0
The ground state energy of a two-electron system corrected to the 1st order
(0) (1) Z 2 e2 5 Ze 2
EG = EG + EG = +
( 4 0 ) a0 8 ( 4 0 ) a0

Level scheme of two-electron atoms

S= S1 + S 2 , and the q. nos. corresponding to S 2 and Sz are S and M S , their possible values

are s1 s2 S s1 + s2 and S MS S .

s1 = s2 = 1
2
S = 0 or 1 2 S + 1 = 1 or 3

In two-electron systems, only spin singlet and spin triplet states are formed.
 66

L= L1 + L2 , and the q. nos. corresponding to L2 and Lz are L and M L , their possible values

are l1 l2 L l1 + l2 and L ML L .

Depending on the values of l1 and l2 , the total orbital quantum number L can have values 0, 1, 2, ....
and the resultant orbital angular momentum states have the designations S, P, D, .......
L = 0, 1, 2,.................

S, P, D............ Resultant orbital angular momentum states

If J= L + S , and if the q. nos. corresponding to J 2 and J z are J and M J , their possible

values are L S J L+S and J MJ J .

2 S +1
The Term Symbol, LJ is used to denote the resultant angular momentum states.

To obtain the level scheme, one electron is kept in the ground state (1s) and the second
electron is moved to higher states starting from the ground state. The resultant angular
momentum states are then characterized as n 2 S +1LJ , where n is the principle q. no. of the
second electron
When both electrons are in their ground state,

Electron configuration: 1s 2 = 1s1s l1 = 0 and l2 = 0 L = 0 only

1
For singlet states, S = 0, L = 0 J =0 S0
3
For triplet states, S =1, L = 0 J =1 S1

When one electron is in its ground (1s) state and the other is in any ns (n = 2, 3, 4, ..) state,
Electron configuration: 1s ns l1 = 0 and l2 = 0 L = 0 only
1
For singlet states, S = 0, L = 0 J =0 S0
3
For triplet states, S =1, L = 0 J =1 S1

When one electron is in its ground (1s) state and the other is in any np (n = 2, 3, 4, ..) state,
Electron configuration: 1s np l1 =0 and l2 =1 L =1 only
1
For singlet states, S =0, L =1 J =1 P1
3
For triplet states, S =1, L =1 J =0, 1, 2 P0 , 3 P1 , 3 P2

Ex: Repeat the above procedure by considering the excited electron configurations 1s nd and
1s nf and write down the possible resultant angular momentum states.
 67

We see that, except for 3S states, for 3 P, 3 D, 3 F states, three values for J are possible. In

the presence of spin-orbit interaction, each of 3 P, 3

D, 3
F state is split into three

closely spaced levels according to the J value. For eg 3P0 , 3P1 , 3P2 ; 3
D1 , 3D 2 , 3D 3 etc.

In two-electron atoms with low Z ( 25) values, the spin-dependent interactions (spin-orbit
and spin-spin) are relatively weak Under electric dipole selection rules,
S = 0, L = 0, 1, transitions from singlet states to triplet states are forbidden.
Therefore, for such two-electron atoms (ions), we can expect two nearly independent systems
of levels corresponding to Para (singlet) and Ortho (triplets) states. In He, these two are
called parahelium and orthohelium. The ground state is necessarily parahelium and the
excited states come in both forms. Since symmetric spatial states bring electrons closer
together, higher interaction energy is expected in parahelium. This is confirmed
experimentally by the fact that, parahelium states have higher energy than their
corresponding orthohelium states.

According to the above figure

 68

(
E He + ) 0 eV and E ( He )
= 24.6 eV
= E He +
Ip = ( ) E ( He ) =
24.6 eV

Similar spectra are expected for two electron ions with Z >2.

When both electrons are in their ground (1s) state,

n1 =
n2 =
1, l1 =
l2 =
0, ml1 = 0 (0) ( r1 , r2 ) =
ml2 = 0 and +(0) ( r1 , r2 ) 0 .

This is in agreement with the Pauli exclusion principle, because, otherwise both electrons will
have all five ( n, l , ml , s and ms ) quantum numbers the same.

# n1 l1 ml1 s1 ms1 n2 l2 ml2 s2 ms2

1 1 0 0 1
2 + 12 1 0 0 1
2 + 12
2 1 0 0 1
2 + 12 1 0 0 1
2 12
3 1 0 0 1
2 12 1 0 0 1
2 + 12
4 1 0 0 1
2 12 1 0 0 1
2 12

Electrons must have at least one quantum number different, i.e. electrons must have different
(anti-parallel) spins, thus allowing the formation of only the singlet state and not the triplet
state in the ground level. The absence of ground level triplet state in the He spectrum led W.
Pauli to propose his famous exclusion principle.

In calculating quantities related to atoms, sometimes it is more convenient to use a new

system of units called atomic units. In atomic units,

me
= 9.11 1031 kg = 1 a.u. of mass,
e = 1.60 1019 = 1 a.u. of charge,
= 1.05 1034 J s = 1 a.u. of angular momentum,
0 8.85 1012 F m 1 = 1 4 a.u.,
permittivity of free space,=
a0 = 5.29 1011 m = 1 a.u. of length

12 a.u. =
The ground state energy of H (Z = 1, n = 1), E1 = 13.6 eV 27.2 eV = 1 a.u. of

energy.
The TISE for a two-electron atom takes the form
1 2 1 2 Z Z 1
r1 r2 + (r1 , r2 ) =E (r1 , r2 )
2 2 r1 r2 r12

Normalized zero-order spatial wave function for the ground state

 69
12
Z 3 Z ( r1 + r2 ) Z3
(0)
0 ( 1 2)
r , r = 1s ( 1 ) 1s ( 2 )
r r = e , where 1s ( ri ) = e Z ri a.u.

Z2 1 1 ( )
En(0) E0( 0) =
0 2
=
+ a.u. E= n2 1 = Z a.u.
n
2 n1 n22
1 2 2 n1 1,=

For He ( Z =
2) E0( 0) =
4.0 a.u., E0exp =
2.90 a.u.
=I P( 0) 2.0 a.u,
= I Pexp 0.90 a.u.
The calculated energy is lower than the experimentally measured values because we have
1
neglected the Coulomb repulsion term .
r12
1
As Z increases, we get a better agreement because the importance of becomes smaller.
r12

Eg .: For C 4+ ( Z =
6) , E0( 0) =
36 a.u., E0exp =
32.4 a.u.
1) ,
For H ( Z = E0( 0) =
1 a.u., E0exp =
0.528 a.u.

Z 2 e2 1 1
Using the energy expression En(1 n)2 =
0
+ , we can obtain the zeroth-order
( 4 0 ) 2a0 n12 n22
energy spectrum for He. In this spectrum, the states for which both electrons are excited
( n1 2, n2 2 ) lie above the ground state energy of the He+(1s) ion plus a free electron.

The variational method

This method consists of guessing trial wave functions which depend on a certain number of
free parameters and then adjusting these parameters until the best solution is obtained. It is
useful in obtaining approximate bound-state energy (an upper bound) and wave functions of a
time-independent Hamiltonian.
The proper form of the trial function depends on the specific problem which is investigated
and is constructed to have as many features of the exact wave function as possible. Unless a
high accuracy is required, trial wave functions can be constructed so that they lead to simple
calculations. Otherwise, trial functions containing many variational parameters will be
necessary.

Consider = ( r , c1 , c2 , c3 , ..........) , where c1 , c2 , c3 , ......... are variational parameters.

H
E ( )
= = E ( c1 , c2 , c3 , .......) (proof is not necessary)

 70
E E E
Set = = = ....................
= 0
c1 c2 c3

This gives a set of coupled equation which can be solved to get c1 , c2 , c3 , .........

Eg: In obtaining the zero-order wave function for 2-electron atoms (ions) we had assumed
that each electron moves in the fully unscreened Coulomb field of the nucleus. However,
in reality, each electron moves in a screened field of the nucleus and this screened effect
can be taken in to account (approximately) by choosing the one-parameter trial function
(normalized).
3
1 c
(=
c, r1 , r2 ) exp c ( r1 + r2 ) a0
a0

2 2 2 2 Ze 2 Ze 2 e2
H = r r + , r12 = r1 r2
2me 1 2me 2 ( 4 0 ) r1 ( 4 0 ) r2 ( 4 0 ) r12

E (c) = ( c, r1 , r2 ) H ( c, r1 , r2 ) d r1 d r2
*
Then ,

5 e2
= c 2 2 Z c + c (Show this)
8 ( 4 0 ) a0
2
dE 5 5 e2
=0 c =
Z Emin =
Z
dc 16 16 ( 4 0 ) a0
This gives an upper bound for the ground state energy. The accuracy of this value can be
increased by including more variational parameters in the trial function.
For a He atom, the ground state energy corrected for screening effect, using variational
method
2 2
5 e2 5
E = 2 = 2 2 13.6 eV = 77.5 eV
16 ( 4 0 ) a0 16

The unperturbed ground state energy

Z 2 e2
E ( ) =
0
= 4 2 13.6 eV = 108.8 eV
( 4 0 ) a0
5 2 e2 5
The first order correction, E ( ) =
1
= 2 2 13.6 eV = 34 eV
8 ( 4 0 ) a0 8

E( ) + E( ) =
0 1
E = 74.8 eV , Experimental value = 79 eV.
So, the variational method provides a more accurate value than the first-order perturbation
theory.
 71
Time-dependent Perturbation Theory
H H 0 + H (t )
Total Hamiltonian of a system, =

H 0 - time-independent Hamiltonian, H (t ) - time-dependent perturbation

0 < < 1 and = 1 for the real physical problem. As 0 H H 0

( 0) ( 0) ( 0)
As done before, assume that the solutions to TISE H 0 k = Ek k are known and k( )
0

form an orthonormal complete set. Since H 0 is independent of time, k( ) and Ek( ) are
0 0

independent of time.

0 (t )
The general solution to the unperturbed TDSE, i = H 0 0 (t ) is
t
0 (t )
= Ck( ) k( ) exp ( i Ek( )t
k
0 0 0
)
...................... (1)

The constants Ck( ) are independent of time. Since k( ) s are orthonormal, if 0 (t ) is

0 0

normalized to unity, then

2 2
( 0) ( 0)
Ck
= k 0 (t ) - Probability that the system in state 0 (t ) being in the

unperturbed state k( ) .
0

2
( 0)
Ck( ) is the corresponding probability amplitude, and
0
Ck =1
k
Since H is time-dependent, it is not possible to find stationary state solutions to
(t )
i = H (t ) and therefore, it is meaningless to find corrections to energy eigenvalues.
t

Since k(0) s from a complete set, the general solution to TDSE is

= (t ) Ck ( t ) k(0) exp ( iEk(0) t )

.................... (2)
k

Coefficients Ck ( t ) are functions of time.

2 2
As before, C=
k (t ) k(0) (t ) - probability that the system in state (t ) being found

in the unperturbed state k( ) at time t.

0

2
Ck ( t ) is the corresponding probability amplitude and Ck (t ) =1
k

By comparing expressions (1) and (2), we see that

0 ( or H (t ) 0 ) H H 0 Ck (t ) Ck(0)

Ck(0) are the initial values Ck (t ) which specify the system before the perturbation is applied.
 72
(t )
To find Ck (t ) , substitute for (t ) in equation i = H (t ) using equation (2),
t

i C k (t ) k(0) exp(iEk(0) t ) + Ck (t ) Ek(0) k(0) exp(iEk(0) t )

k k

H 0 + H (t ) Ck (t ) k(0) exp(iEk(0) t )
=
k

( 0) ( 0) ( 0)
Since H 0 k = Ek k ,

i C k (t ) k(0) exp(
= i Ek(0) t ) H (t ) Ck (t ) k(0) exp(i Ek(0) t )
k k

Multiplying throughout by b(0)* ( belonging to the set { }) , integrating and using the
( 0)
k

fact that b(0) k(0) = bk ,

Cb (t ) = ( i ) H bk
1
( )
(t ) exp ibk t Ck (t ) .................. (3)
k

Eb(0) Ek(0)
(t ) =
where H bk b(0) H k(0) , Bohr angular frequency, bk =

The set of first-order coupled differential equations given by equation (3) is equivalent to the
TDSE. For any value of b , C b (t ) depends on all k(0) connected with b(0) via H bk
(t ) .

Now assume that H (t ) is weak and expand Ck (t ) in powers of .

i..e Ck (t ) = Ck(0) (t ) + Ck(1) (t ) + 2 Ck(2) (t ) + .................

Substituting this in equation (3) and equating the coefficients of equal powers of , we get
Cb(0) (t ) = 0

Cb(1) (t ) = ( i ) H bk
1
(
(t ) exp ibk t Ck(0) (t ) )
k

. .
..
..

(t ) exp ( ibk t ) Ck( s ) (t ),

i ) H bk
1
Cbs +1 (t ) (= s 0, 1, 2, .......
k

Cb(0) (t ) = 0 Ck(0) s are independent of time. ( Ck(0) s define the initial conditions of

the problem)
 73

Assume that the system is initially (at t0 and usually t0 = 0 ) in the unperturbed state a(0) of

energy Ea(0) 0 = a(0) .

Ck(0)
= k(0) =
0 k(0) a(0)= k a ( if a(0) is discrete )

= ( k a ) ( if a(0) is continuous )

Initially Ca(0) = 1 and all other coefficients Ck(0) (with k a) vanish.

Substituting for Ck(0) in the expression of Cb(1) (t ) ,

Eb(0) Ea(0)
(t ) exp ( ibk t ) ka
i ) H bk
1 1
Cb(1) (t ) (= ( i ) =
H ba (t ) exp(iba t ), where ba
k

t
1
Solution
= Ca(1) (t ) (=
i ) H a a ( t ) dt , if b a
t0

t
=Cb(1) (t ) ( i )1 H ba ( t ) exp ( iba t )dt , if b a .. (4)
t0

where Ca(1) (t ) and Cb(1) (t ) have been chosen to be equal to zero at t = t0 (before the
perturbation is applied)
Expression (4) provides the expansion coefficients in ( t ) in the first-order.

To first-order in perturbation, the transition probability of the transition a b (i.e. the

probability that the system, initially in eigenstate a of H 0 to be found at time t in the

2
eigenstate b ( a ) ), Pb(1)a (t ) = Cb(1) (t )

2
t
Pb(1)a (t ) H ba ( t ) exp ( iba t ) dt
2
= , ba
t0

For t > t0 , the coefficients Ca (t ) of the state a, given to 1st order in perturbation,

(C (0)
k = k a Ca(0) =1 )
1
t i t
Ca (t ) Ca(0) + Ca(1) (t ) 1 + ( i ) aa
H ( t ) d t exp aa
H (t )d t ........ (5)

t0 t0
2
Ca ( t ) 1 (the perturbation changes the phase of the initial state.)
 74

Tutorial 3
11. A one-dimensional harmonic oscillator of charge e is perturbed by an electric field of
strength E in the positive x-direction. Calculate the change in energy level to second order in
the perturbation, and calculate the induced electric dipole moment. Show that this problem
can be solved exactly, and compare the result with the perturbation approximation. Repeat
the calculation for a three-dimensional isotropic oscillator. Show that, if the polarizability
of the oscillator is defined as the ratio of the electric dipole moment to E, the change in
energy is exactly E2/2.

12. Consider the Hamiltonian, H = p x2/2m + kx2/2 + x2/2, k > 0. (a) Find the exact energy of the
nth state of this Hamiltonian and expand it to order 2 assuming < k. (b) Use perturbation
theory, treating x2/2 as a perturbation, and find the energy of the nth state to order 2.

13. A one-dimensional harmonic oscillator is perturbed by an extra potential energy x3.

Calculate the change in each energy level to second order in the perturbation.

14. Find the approximate ground state energy to second order for the Hamiltonian, H = px 2/2m +
kx2/2 + x4/4 using perturbation theory.

15. Find the shift in the energy of the n = 1 level of a hydrogen atom, to second order due to a
constant electric field (linear Stark effect). The potential is V' = eEz.

16. A particle is in a two-dimensional box of sides a. If a perturbation V' = sin(mx/a)sin(ny/a)

is applied calculate to second order the shifts in the energy levels of the ground state and the
first excited state.

17. Two particles of mass m are placed in a rectangular box of sides a < b < c in the lowest
energy state of the system compatible with the conditions below. Assuming that the
particles interact with each other according to the potential V = V0 (r 1 r 2 ), use first order
perturbation theory to calculate the energy of the system under the following conditions: (a)
Particles not identical. (b) Identical particles of spin zero. (c) Identical particles of spin one-
half with spins anti-parallel. (d) Identical particles of spin one-half with spins parallel.

18. A system that has three unperturbed states can be represented by the perturbed Hamiltonian
E1 0 a

matrix 0 E2 b . The quantities a and b are to be regarded as perturbations that are
a * b* E
3

small compared with E1 , E2 and E3 . Use the first and second order non-degenerate
perturbation theory to calculate the perturbed eigenvalues Then, diagonalize the matrix to
find the exact eigenvalues.

19. Show that the 1st order energy shift (1st order Stark effect) for the ground state of a hydrogen
atom is zero. Find an approximated value for the 2nd order energy shift (2nd order Stark
effect) for the ground state. Also, find the 1st order energy shift for the 1st excited state.
(See, lecture notes.)

20. Find the expressions for the 1st order energy shifts of hydrogenic energy levels due to
relativistic effects. (see lecture notes)
 75

21. Find an expression for the zeroth-order energy of the ground state of a two-electron atom in
terms of the ground state energy of a hydrogenic atom. Construct a suitable zeroth-order
wave function for the ground state of a two electron atom in terms of hydrogenic atom wave
functions. Then, use this to obtain an expression for the 1st order correction to energy of the
ground state of a two-electron atom. Simplify your answer until you get some integrals over
position co-ordinates which are difficult to evaluate. (See lecture notes.)

22. For a spin- 12 particle, find the eigenvalues and corresponding eigenfunctions of S x and S y
in the basis consisting of the two basic spin - 12 states and of S z . (Use the matrix
forms of S x , S y and S z give in class notes.)

23. Suppose that an electron beam polarized in the positive z-direction is sent through an Stern-
Gerlach analyzer which measures S x . What values will be found and with what
probabilities will these values occur ?
2
24. Use the trial wave function (normalized) ( x, c) = N e c x , where c is the variational
parameter and N is the normalization constant, to estimate the ground state energy of a
linear harmonic oscillator of mass m oscillating with angular frequency along the x-
axis.

25. Consider two non-interacting, indistinguishable fermions of spin- 12 , each of mass m,

confined to a one-dimensional, infinitely deep, square potential well of width a, which is
defined as the potential energy V(x) = 0 for 0 x a and V(x) = + elsewhere. Write down
the wave functions (spatial) and corresponding energy values of the two-particle states.
Hence, obtain the relevant full wave functions and corresponding energy values of the spin
singlet and spin triplet states, formed by the two-particle ground state and by the two-particle
first excited state.
76
 77

The Schrodinger equation for 2-electron atoms takes the form (assuming M is very large)
2 2 2 2 Ze 2 Ze 2 e2
r1 r2 (r1 , r2 ) =E (r1 , r2 ),
2me 2me (4 0 )r1 (4 0 )r2 (4 0 )r12

r12= r1 r2 , (r1 , r2 ) - Spatial part of the two-electron wave function
----------------------------------------------------------------------------------------------------------------
----
Here it is more convenient to use a new system of units called atomic units. In atomic units,

me
= 9.11 1031 kg = 1 a.u. of mass,
e = 1.60 1019 = 1 a.u. of charge,
= 1.05 1034 J s = 1 a.u. of angular momentum,
0 8.85 1012 F m 1 = 1 4 a.u.,
permittivity of free space,=
a0 = 5.29 1011 m = 1 a.u. of length

12 a.u. =
The gnd. state energy of H (Z = 1, n = 1), E1 = 13.6 eV 27.2 eV = 1 a.u. of

energy
----------------------------------------------------------------------------------------------------------------
----
1 2 1 2 Z Z 1
r1 r2 + (r1 , r2 ) =E (r1 , r2 )
2 2 r1 r2 r12

This equation is unchanged under the interchange of r1 and r2 .

both (r1 , r2 ) and (r2 , r1 ) satisfy the same Schrdinger equation.

If (r2 , r1 ) = (r1 , r2 ) the wave function is space symmetric and is denoted by

+ (r1 , r2 ) , called Para States

If (r2 , r1 ) = (r1 , r2 ) the wave function is space anti-symmetric and is denoted by

(r1 , r2 ) , called Ortho States

In oneelectron atoms, the electron spin only affects the fine structure and hyperfine structure
of the spectrum. In two-electron atoms, the spin of the two electrons influence the spectrum
as required by the Pauli exclusion principle.
The full wave function (q1 , q2 ) can be written as

(q1 , q2 ) = (r1 , r2 ) (1, 2) ,
Spatial wave Two-electron Spin
function wave function
 78

where q1 and q2 denote the space and spin co-ordinates of each electron.

In the absence of spin-dependent interactions, each electron spin can be directed either up ()
or down () independent of the other. , , ,

Suppose S1 and S 2 are spin operators of the two electrons and S1z and S2 z are the z-

components. Let (1) and (1) are basic spin functions associated with S 12 and S1z , and

(2) and (2) are basic spin functions associated with S 2 and S2 z . The four possible spin
2

orientations and corresponding spin functions are

(1) (2), (1) (2), (1) (2), (1) (2)

S= S1 + S2 S z =
S1z + S2 z s1 = 1
s2 =
2

S s1 s2 M S ms1 ms2 ms1 = ms2 = 12

If S and M S are the quantum numbers corresponding to the resultant spin operator S and its

z-component S z . (Note: Q. nos of resultant angular momentum states are denoted by Capital
letters.)
Since s1 s2 S s1 + s2 S=
0 and 1

Since S M S S , for S =
0 MS =
0 and for S =
1 MS =
1, 0, 1
(Also note that, M=
S mS1 + mS2 )

When S= 0 2S + 1= 1 and such states are called Spin Singlet states.

When S = 1 2S + 1= 3 and such states are called Spin Triplet states.
 79

We can construct four (normalized and mutually orthogonal) resultant spin functions

S , M S (1, 2) which are eigenstates of S 2 and Sz , of the two-electron system.

1
S=
0, M S =
0 0, 0 (1, 2) =[ (1) (2) (1) (2)] Anti-symm. spin function (spin singlet)
2

S=
1, M S =
+1 1, 1 (1, 2) = (1) (2)
1
0 1, 0 (1, 2)= [ (1) (2) + (1) (2)] Symmetric spin functions (spin triplet)
2
1 1, 1 (1, 2) =
(1) (2)

Pauli exclusion principle requires that the total wave function (q1 , q2 ) of the system of two
electrons must be anti-symmetric under the interchange of spin and spatial co-ordinates of
electrons. Under this, we can construct the total anti-symmetric wave functions as follows.
1
( q1 , q2 ) = + (r1 , r2 ) [ (1) (2) (1) (2)] Para wave function (spin singlet)
2

(1) (2)

1
( q1 , q2 ) = (r1 , r2 ) [ (1) (2) + (1) (2)] Ortho wave function (spin triplet)
2
(1) (2)

Level scheme of 2-electron atoms

Under electric dipole selection rules, transitions from singlet states to triplet states are
forbidden. This is valid for atoms (ions) with Z 40, in which the spin-orbit interaction can
be neglected.
 80
Therefore, for such two-electron atoms (ions), we can expect two nearly independent systems
of levels corresponding to Para (singlet) and Ortho (triplets) states.
In He, these two are called Parahelium and Orthohelium.

If L= L1 + L2 , and if the q. nos. corresponding to L2 and Lz are L and M L , their possible
values are
l1 l2 L l1 + l2 and L ML L .

Depending on the values of l1and l2 , the total orbital quantum number L can have values 0, 1, 2, .......
L = 0, 1, 2,.................

S, P, D............ Resultant orbital angular momentum states

If J= L + S , and if the q. nos. corresponding to J 2 and J z are J and M J , their possible
values are
L S J L+S and J MJ J .
2 S +1
The Term Symbol, LJ is used to denote the resultant angular momentum states.
For singlet ( S = 0 ) states, L = 0 J = 0 , L =1 J =1 , L =2 J = 2 etc.
(i.e. for each value of L, a single value for J is possible)
For triplet ( S = 1 ) states, L = 0 J =1 , L =1 J =0, 1, 2 ,
L =2 J =1, 2, 3 etc.
(i.e. except for S states, for P, D, F states, three values for J are
possible)
Therefore, 3 P, 3
D, 3
F states are split into three closely spaced levels, under the

influence of spin-orbit and spin-spin interactions. For eg: 3P0 , 3P1, 3P2 ; 3
D1, 3D 2 , 3D 3

etc.
 81

Transitions occur under the selection rules S = 0, L = 0, 1 .

According to the above figure

(
E He + ) 0 eV and E ( He )
= 24.6 eV
= (
E He +
Ip = ) E ( He ) =
24.6 eV

Similar spectra are expected for two electron ions with Z >2.

The independent particle model

1 Z 1 Z 1 1
H = 2r1 2r2 + = H 0 + H , where H = and
2 r1 2 r2 r12 r12
1 Z
H 0 = h1 + h2 , hi = 2ri (with i = 1, 2)
2 ri

are hydrogenic atom Hamiltonians with normalized eigenfunctions ni li ml ( ri ) and energies
i

Eni .

1 Z2
hi nili ml ( ri ) = Eni nili ml ( ri ) , Eni = (a.u.)
i i 2 ni2

Neglecting H , the zero-order TISE equation and its solutions can be written as

H 0 ( 0) ( r1 , r2 ) = E ( 0) ( 0) ( r1 , r2 ) , where

( 0) ( r1 , r2 ) = n1 l1 ml ( r1 ) . n2 l2 ml ( r2 ) and
1 2

( 0) ( 0) Z2 1 1
E = E n1 n2 = En1 + En2 = 2 + 2 .
2 n1 n2
0
We see that ( ) ( r2 , r1 ) = n2 l2 ml ( r1 ) n1 l 1ml ( r2 ) is also an eigenfunction of H 0 with the
2 1

same energy E ( ) n1n2 . This degeneracy which occurs under exchange of electron labels is
0

1
called the exchange degeneracy. It is removed when the term is taken into account.
r12

The proper (zero order) spatial functions

1
(0) ( r1 , r2 ) n1l1ml ( r1 ) n2l2ml ( r2 ) n2l2ml ( r1 ) n1l1ml ( r2 )
2 1 2 2 1

Are symmetric or anti-symmetric under interchange of r1 and r2 .
 82

Both +(0) ( r1 , r2 ) and (0) ( r1 , r2 ) correspond to the same energy En(0)
1 n2
(Show this )

When both electrons are in the ground state,

n1 =
n2 =
1, l1 =
l2 =
0, ml1 = 0 (0) ( r1 , r2 ) =
ml2 = 0 and +(0) ( r1 , r2 ) 0

This is in agreement with the pauli exclusive principle.

Otherwise, both electrons will have all five ( n, l , ml , s and ms ) quantum numbers the same.

electrons must have at least one different quantum number.

electrons must have different (anti-parallel) spins.

Only the singlet (para) state is allowed and ground state triplet level of He is absent.

Normalized zero-order spatial wave function for the ground state

Z3
= ( r1 , r2 )
= 100 ( r1 ) 100 ( r2 ) = 1s ( r1 ) 1s ( r2 )
(0)
0 e Z ( r1 + r2 )

1
Z 3 2 Z ri
where 100 ( ri ) = 1s ( ri ) = e

( )
E0( 0) =
0 2
E= n2 1 = Z a.u.
n1 1,=

For He( Z =
2) E0( 0) =
4.0 a.u., E0exp =
2.90 a.u.
=I (p0) 2.0 a.u,
= I pexp 0.90 a.u.

The calculated energy is lower than the experimentally measured values because we
1
have neglected the Coulomb repulsion term .
r12
1
As Z increases, we get a better agreement because the importance of becomes
r12
smaller.

e.g.:- For C 4+ ( Z =
6) , E0( 0) =
36 a.u., E0exp =
32.4 a.u.
H (Z =
1) , E0( 0) =
1 a.u., E0exp =
0.528 a.u.

Z2 1 1
Using the energy expression E ( ) n1n2 =
0
2 + 2 we can obtain the energy
2 n1 n2

spectrum for He. In this spectrum, the states for which both electrons are excited
( n1 2, n2 2 ) lie above the ground state energy of the He+(1s) ion plus a free

electron.
83