Chapter 9 R17

Non-degenerate Perturbation Theory
Problem :
H  n  En  n
can't solve exactly.
But
0
H  H   H '  2 H "
with
0
Lim   0 H  n0  En0  n0
Unperturbed eigenvalue problem.

Can solve exactly.
Therefore, know E n and  n .
0 0
 H '  2 H "
called perturbations
Copyright – Michael D. Fayer, 2017
Solutions of
0
H  n0  En0  n0
complete, orthonormal set of ket vectors
 
0
n  00 , 10 ,  20 
0 0 0
with eigenvalues E0 , E1 , E2 , 
and
 n0  m0   mn
Kronecker delta
1 n  m
 nm  
0 n  m

Expand wavefunction
 n   n0    n   2  n 
and
En  En0   En   2 En 

also have
0
H  H   H '  2 H "
Have series for
H n En
Substitute these series into the original eigenvalue equation
H  n  En  n

Sum of infinite number of terms for all powers of l equals 0.
H 0
 
 n0  En0  n0  0  H  n  H '  n0  En0  n  En'  n0 
0


 H  n  H '  n  H "  n0  En0  n  En  n  En  n0  2
0

 0
Coefficients of the individual powers of l must equal 0.
zeroth 0
order - l0 H  n0  En0  n0  0
first
H  n  H '  n0  En0  n  En  n0  0
0
order - l1
second
H  n  H '  n  H "  n0  En0  n  En  n  En  n0  0
0
order - l2

First order correction
H  n  En0  n   E n  H '  n0
0
Want to find E n and  n .
Expand  n
 n   ci  i0 also substituting
i
Then
H  n   ci H  i0   ci Ei0  i0
0 0
Substituting this result.
i i
After substitution
c  E
i
i
0
i 
 En0  i0   En  H '  n0

After substitution
c  E
i
i
0
i 
 En0  i0   En  H '  n0
Left multiply by
 n0
 n0 i i n i
c E 0
 E 0
 0

  0
n  E 
n  H 
'   0
n
i
c  E
i
i
0
i 
 E n0  n0  i0   n0  En  H '  n0
 n0  i0  0 unless n = i,
but then
E n0  E n0  0
Therefore, the left side is 0.

We have
 n0  En  H '  n0  0
 n0 En  n0   n0 H '  n0  0
E n number, kets normalized, and transposing,
E n   n0 H '  n0 The first order correction to the energy.

  0
(Expectation value of H in zeroth order state n )
Then
En  En0   En
 and En
Absorbing l into H nn
En  En0  En
En   n0 H '  n0  Hnn
The first order correction to the energy is the expectation value of H ' .
First order correction to the wavefunction
Again using the equation obtained after substituting series expansions
c  E
i
i
0
i 
 En0  i0   En  H '  n0
Left multiply by  0j
 0j c  E
i
i
0
i 
 En0  i0   0j  En  H '  n0
Equals zero unless i = j.
 
c j E 0j  En0   0j  En  H '  n0
 
c j E 0j  En0    0j H '  n0
 0j H '  n0
cj  jn
E 0
n E 0
j 
Coefficients in expansion of ket in terms of the zeroth order kets.
 0j H '  n0
cj  jn
E 0
n E 0
j 
H 'jn
cj  H 'jn is the bracket of H ' with  0j and  n0 .
E 0
n E 0
j 
correction to zeroth order ket

Therefore
H jn The prime on the sum mean
n   0
n  '  0
j
j ( En  E j ) j  n.
0 0
zeroth order ket
energy denominator

First order corrections
E n  En0  Hnn'   Hnn'   n0 H   n0
H jn
n   0
n  '  j 
0
H jn   0j H   n0
j ( En  E j )
0 0

Second Order Corrections
Using l2 coefficient
Expanding  n  n
Substituting and following same type of procedures yields
H ni H in l2 coefficients have been absorbed.

E n   ' 
 H nn
i  En  Ei
0
0
H ni H in   n0 H   i0  i0 H   n0
Second order correction due Second order correction due to an

to first order piece of H. additional second order piece of H.
 
 H mn
H km  H nn H kn
 H 
 n  '   ' 0    k0   ' 0 kn 0  k0
k  m


En  E k0 En0  Em0 E 0
n
 
 E 0
k 
2

 k ( En  Ek )
Second order correction due Second order correction due to an

to first order piece of H. additional second order piece of H.
Energy and Ket Corrected to First and Second Order
H ni H in
E  E  H 'nn  
0 '   
 H nn
i
0

En  Ei 0

H jn  
 H mn
H km  H nn H kn

n   0
 ' 0  0
 
'  '    k0
n
j ( E n  E 0
j )
j
k 

m  0

En  Ek En  Em
0 0 0
 
E 0
n  E 0
k 
2


H 
  ' 0 kn 0  k0  
k ( En  Ek )

Example: x3 and x4 perturbation of the Harmonic Oscillator
Vibrational potential of molecules not harmonic.

Approximately harmonic near potential minimum.
Expand potential in power series.
First additional terms in potential after x2 term are x3 and x4.

2
p 1 2 3 4
H  k x  cx  qx
2m 2
quartic “force constant”
cubic “force constant”
2
0 p
1 2
H   kx harmonic oscillator – know solutions
2m 2
H 
0 1
2



  aa  a a 
 1
E 0   n    0 zeroth order eigenvalues
 2
n zeroth order eigenkets
3 4
H '  cx  qx perturbation
c and q are expansion coefficients like l.
When c and q  0, H  H 0
  n H' n
H nn
3 4
 n cx  qx n
3 4
c n x n q n x n
In Dirac representation
1
  
 
2
x 0 a  a
 2k 
First consider cubic term.
 
3
3 
x  aa
Multiply out. Many terms.

3 2   3
a , a a , aa a ,  a .
None of the terms have the same number of raising and lowering operators.
3
n x n 0 (At second order will not be zero.)
 2 02
 
4
4 
n x n  n a  a n
4k 2
aa 
4

has terms with same number of raising and lowering operators.
4
Therefore, n x n 0
Using a n  n1/ 2 n  1 and a  n  ( n  1)1/ 2 n  1
n aaa  a  n   n  1  n  2 
n a  a  aa n  n  n  1
Only terms with the same number of
raising and lowering operators are
n aa  aa  n   n  1
2
non-zero.
n a  aa  a n  n2 There are six terms.
n aa  a  a n  n  n  1
n a  aaa  n   n  1 n
Sum of the six terms
 
4

n aa n  6( n2  n  1 2)
Therefore
q  2 02 3  2 1
 
H nn n  n 
k 2 2  2 
With 0  k m k 2   04 m 2
 1 3 2 1  2
En   n    0  q  n  n   2 2
 2 2 2  m 0
Energy levels not equally spaced.

Real molecules, levels get closer together – q is negative.
Correction grows with n faster than zeroth order term
decrease in level spacing.

Perturbation Theory for Degenerate States
H 1  E 1 1 and  2
normalize and orthogonal
H 2  E 2
1 and  2 Degenerate, same eigenvalue, E.
If   c1 1  c2  2
with c1c1  c2 c2  1
H E
Any superposition of degenerate eigenstates is also an eigenstate

with the same eigenvalue.

n linearly independent states with same eigenvalue
system n-fold degenerate
Can form n orthonormal  i from the n degerate  n .
Can form an infinite number of sets of  i .

Nothing unique about any one set of n degenerate eigenkets.

Want approximate solution to
H 0

  H '  j  Ej  j
zeroth order perturbation

Hamiltonian
 0 0
H  0j  E 0j  0j
zeroth order zeroth order

eigenket energy
But E i0 is m-fold degenerate.

Call these m eigenkets belonging to the m-fold degenerate E10
10 ,  20   m0 orthonormal
With E10  E20    Em0  E10

Here is the difficulty
 0
 i   i0
0
perturbed ket zeroth order ket having eigenvalue, E1

But, i
0
is a linear combination of the  i .
0
 i0  c1 10  c2  20    cm  m0
We don’t know which particular linear combination it is.
 i0 is the correct zeroth order ket, but we don’t know the ci.
The correct zero order ket depends on the nature of the perturbation.
p states of the H atom in external
magnetic field – p1, p0, p-1
electric field – px, pz, py
To solve problem
Expand E and  i E  E10   E   

m
 i   c j  0j    i  
j 1
Some superposition, but we don’t know the cj.

Don’t know correct zeroth order function.
Substituting the expansions for E and  i into
 0
H   H '  i  Ei  i
and obtaining the coefficients of powers of l, gives
m m
zeroth
cj   j j
0
H 0
E
0
c  0
order j 1
j 1
j 1
H      c  E   H ' 
m
first 0
E 0 0
1 i j j
order j 1
want these
H      c  E   H ' 
m
0
E
0
1 i j
0
j To solve
j 1
substitute  i   Ak  k
0
Need H '  0j
Use projection operator  k  k
0 0
H '  0j    k0  k0 H '  0j
k
The projection operator gives the piece of H '  j that is  k .

0 0
Then the sum over all k gives the expansion of H '  j in terms of the  i .
0 0
Defining H kj'   k H '  j

0 0
Known – know perturbation piece of the
Hamiltonian and the zeroth order kets.
H '  0j   H kj  k0
k

H '  0j   H kj  k0
H      c  E   H ' 
m
0
E 0
1 i j
0
j k
j 1
this piece becomes

m m
c H 
j 1
j
0
j   c j H kj  k0
j 1 k
Substituting this and  i   Ak  k

0
gives
k
m  m  0
 E 0
k  E Ak 
0
1  0
k   E c j  0
j     c j H kj   k
k  j 1
k j 1 
Result of operating H0 on the zeroth order kets.
Left multiplying by  i0
m  m  0 0
 E 0
k 1 
 E Ak  
0 0
i
0
k   E c j   0
i
0
j     c j H kj   i  k
k  j 1

k j 1 

m  m  0 0
 E 0
k 1 
 E Ak  
0 0
i
0
k   E c j   0
i
0
j     c j H kj   i  k
k  j 1

k j 1 
Correction to the Energies
Two cases: i  m (the degenerate states) and i > m.
i  m
Left hand side – sum over k equals zero unless k = i.
But with i  m,
E i0  E10 Therefore, Ei0  E10  0
The left hand side of the equation = 0.
Right hand side, first term non-zero when j = i. Bracket = 1, normalization.
Second term non-zero when k = i. Bracket = 1, normalization.
The result is
m
 Hc
j 1
ij j  E ci  0
We don’t know the c’s and the E s .

m
 Hc
j 1
ij j  E ci  0 is a system of m of equations for the cj’s.
 H11  E  c1  H12 c2    H1m cm  0
 c1   H 22
H 21   E   c2    H 2 m cm  0 One equation for
each index i of ci.
H m 1c1  H m 2 c2     H mm
  E   cm  0
Besides trivial solution of c1  c2    cm  0

only get solution if the determinant of the coefficients vanish.
 H11  E  H12  H1m We know the

H jk   0j H   k0
  H 22  E   H 2 m
0
  Have mth degree
equation for the E  s .
H m 1 H m 2   H mm
  E 

Solve mth degree equation – get the E i s . Now have the corrections to energies.
To find the correct zeroth order eigenvectors, one for each E i ,
substitute E i (one at a time) into system of equations.
Get system of equations for the coefficients, cj’s.
 H11  Ei  c1  H12 c2    H1m cm  0

Know the H ij .
 c1   H 22
H 21   E i  c2    H 2 m cm  0
H m 1c1  H m 2 c2     H mm
  Ei  cm  0
There are only m – 1 conditions because can multiply everything by constant.

Use normalization for mth condition.
c1*c1 ,  c2*c2 ,    cm* cm  1
Now we have the correct zeroth order functions.

The solutions to the mth degree equation (expanding determinant) are
E1, E 2,  E m
Therefore, to first order, the energies of the perturbed initially degenerate

states are
E i  E10  Ei 1 i  m
Have m different E i s (unless some still degenerate).
With E i  E10
as  0

Correction to wavefunctions
Again using equation found substituting the expansions into
the first order equation
m  m  0
 E 0
k 
 E10 Ak  k0   E c j  0j     c j H kj   k
k  j 1
k j 1 
Left multiply by
 i0 ikm gives 1 gives 0
Orthogonality makes other terms zero.

Normalization gives 1 for non-zero brackets.
m
E 0
k E 0
1 A k    c j H kj
j 1
m
c H
j 1
j kj
Therefore Ak  km
E 0
1 E 0
k  Normalization gives Aj = 0 for j  m.
Already have part of wavefunction for j  m
First order degenerate perturbation theory results
E i  E10   Ei  
c H j kj
 i   i0    j 1
 k0  
k m E 0
1  E k0 
Correct zeroth order function. Correction to

Coefficients ck determined from zeroth order function.
system of equations.

Chapter 9 R17

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Chapter 9 R17

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Non-degenerate Perturbation Theory

can't solve exactly.

Unperturbed eigenvalue problem.

complete, orthonormal set of ket vectors

Copyright – Michael D. Fayer, 2017

En  En0   En   2 En 

Have series for

Substitute these series into the original eigenvalue equation

Copyright – Michael D. Fayer, 2017

Copyright – Michael D. Fayer, 2017

Want to find E n and  n .

Copyright – Michael D. Fayer, 2017

Therefore, the left side is 0.

Copyright – Michael D. Fayer, 2017

E n number, kets normalized, and transposing,

E n   n0 H '  n0 The first order correction to the energy.

En   n0 H '  n0  Hnn

Equals zero unless i = j.

correction to zeroth order ket

zeroth order ket

Copyright – Michael D. Fayer, 2017

E n  En0  Hnn'   Hnn'   n0 H   n0

Copyright – Michael D. Fayer, 2017

H ni H in l2 coefficients have been absorbed.

Second order correction due Second order correction due to an

Second order correction due Second order correction due to an

Copyright – Michael D. Fayer, 2017

Vibrational potential of molecules not harmonic.

First additional terms in potential after x2 term are x3 and x4.

Copyright – Michael D. Fayer, 2017

n zeroth order eigenkets

First consider cubic term.

Multiply out. Many terms.

Using a n  n1/ 2 n  1 and a  n  ( n  1)1/ 2 n  1

Energy levels not equally spaced.

Copyright – Michael D. Fayer, 2017

1 and  2 Degenerate, same eigenvalue, E.

Any superposition of degenerate eigenstates is also an eigenstate

Copyright – Michael D. Fayer, 2017

Can form n orthonormal  i from the n degerate  n .

Can form an infinite number of sets of  i .

Copyright – Michael D. Fayer, 2017

zeroth order perturbation

zeroth order zeroth order

But E i0 is m-fold degenerate.

With E10  E20    Em0  E10

Copyright – Michael D. Fayer, 2017

We don’t know which particular linear combination it is.

Expand E and  i E  E10   E   

Some superposition, but we don’t know the cj.

The projection operator gives the piece of H '  j that is  k .

Defining H kj'   k H '  j

Copyright – Michael D. Fayer, 2017

this piece becomes

Substituting this and  i   Ak  k

Copyright – Michael D. Fayer, 2017

We don’t know the c’s and the E s .

 H11  E  c1  H12 c2    H1m cm  0

Besides trivial solution of c1  c2    cm  0

 H11  E  H12  H1m We know the

Copyright – Michael D. Fayer, 2017

 H11  Ei  c1  H12 c2    H1m cm  0

There are only m – 1 conditions because can multiply everything by constant.

c1c1 ,  c2c2 ,    cm* cm  1