Department of Physics, IIT Madras

Hartree Fock formalism

PCD_STiAP_P04

1
1. For a two electron system, spin exchange operator is given by Vˆex   K 1  4sˆ1 sˆ2 
2
Where K is the exchange integral and ŝ1 and ŝ2 are spin angular momentum operators of
two electrons. This was first introduced by Dirac and has wide applications in Condensed
Matter Physics.
1
a) Show that sˆ1 sˆ2   Sˆ 2  sˆ12  sˆ2 2 
2
Where Ŝ is total spin operator.
1
b) Show that eigenvalues of sˆ1 sˆ2 for triplet  S  1 and singlet  S  0  states are
4
3
and  respectively.
4
c) Find the eigenvalues of Vex for triplet and singlet states.
d) Show that Vsin glet  Vtriplet  2K .
e) Which is the ground state of the system?

2. Prove that the direct integral J and exchange integral K for a N electron atomic system
are real and positive.

3. For the ground state of an atom or ion having N electrons,

N N
 i2 Z 
H1   f  qi       
i 1 i 1  2 ri 

V  qi , q j   
1 N 1
H2  
2 i , j 1, j i i  j rij

Where H1 is the sum of the N identical one-body hydrogenic Hamiltonian and H 2 is the
N  N  1
sum of identical terms which represent the two-body interactions between each
2
pair of electrons and a and b are Slater determinants,
1
a  q1 , q2 ......qN     1 Pu1  q1  u2  q2  .......u N  qN 
P

N! P
1

b  q1 , q2 ......qN  
 1 Pu1  q1  u2  q2  .......uN  qN 
P

N! P
where P is the permutation operator.
 Prove that:
a) For a  b ,
N
a H1 a   u  qi  f u  qi 
i i
i 1

 [ ui  qi  u j  q j  V ui  qi  u j  q j 
1 N
a H 2 a 
2 i , j 1
 u j  qi  ui  q j  V ui  qi  u j  q j  ] .
b) For a  b
(  k   k and i   i for all i  k )
b H1 a  u  qk  f u  qk 
k k

N
b H 2 a   u  qi  u  qk  V u  qi  u  qk 
i k i k
i 1

 uk  qi  ui  qk  V ui  qi  uk  qk  ]

c) For a  b
( k   k ; k  l ; l  l ; l   k and i   i for all i  k , l
b H1 a  0
N
b H 2 a   u  qk  u  ql  V u  qk  u  ql 
k l k l
i 1

 ul  qk  uk  ql  V uk  qk  ul  ql  .

d) For a  b
(Differing in more than 2 sets of q labels.)
b H1 a  0
b H 2 a  0

4. Prove that the matrix  , made up of Lagrange variational multipliers which constraint the
variation in the elements of Hartree-Fock Slater determinants, is self adjoint.

5.
a) Obtain the condition that H , where H is the N-electron Hamiltonian, is an
extremum subject to the constraint that the one-electron spin-orbitals in the
variational N-electron antisymmetrized wave function are normalized and
orthogonal.
b) Express the above condition in a form in which the matrix of the Lagrange
variational multipliers is diagonal and demonstrate that this condition is expressed
by:
 u*j  r2  u j  r2 
f  r1  uk  r1   [  d 2 ]uk  r1 
j r12
u*j  r2  uk  r2 
j

  msk , ms j [  d 2  r12
]u j  r1 

 kk uk  r1 
  k uk  r1 
Where  k  kk


c) Comment on the factor  msk , ms j in the above equation. 
d) Find the function U k  r1 , r2  such that;
u*j  r2  uk  r2 
 d U  r , r  u  r      m
2 k 1 2 k 2
j
sk 
, ms j [  d 2
r12
]u j  r1 

e) Show that the one-electron Hartree-Fock equation is written in a form inclusive of

the spin variables such that the spin-orbital U k  q   q k has k which represents
a set of 4 quantum numbers including spin is given by:
i2
[  VHF  qi ]uk  qi    k uk  qi 
2
Where
Z
VHF  qi    V c  qi   V ex  qi 
ri
N u*j  q2  u j  q2 
V c
 qi     dq2
j 1 ri 2
N u*j  q2  uk  q2 
V exuk  qi     dq2 u j  qi 
j 1 ri 2

f) Is the Hartree-Fock equation given above an eigenvalues equation?

g) Can you define the Hartree-Fock potential VHF as a function of a single coordinate
(that is, one set of 3 space coordinates and 1 spin coordinate) alone?

6. Determine if the potential U in problem 5(d) is Hermitian.

7.
a) Prove that;
kk  nk k f k  nk  n j [ kj V kj  jk V kj
j

b) If kk is written as  k , prove that:

  
c) E     E nk 0    k
N N 1

[Ref : T.H. Koopmans Physics 1 104 (1933)]
d) Write the Slater determinant for ground state 1s 2 2s 2 1S of beryllium.
 e) The Hartree-Fock potential is given by:
VHF    V1ds  V1ds  V2ds  V2ds  V1exs  V1exs  V2exs  V2exs 
4
ri
Where V d and V ex are direct and exchange integrals respectively.
Obtain the two coupled integro-differential equation:
 1 2 4 
 r   V1s  r   2V2 s  r   V2 s  r  u1s  r   E1su1s  r 
d d ex

 2 r 
 1 2 4 
 r   V2 s  r   2V1s  r   V1s  r   u2 s  r   E2 su2 s  r 
d d ex

 2 r 

8. Prove that  H , L  0 , where H is the Hamiltonian

N
 2 Z  N 1
H    i   + 
i 1  2 ri  i  j 1 rij
And L   Li is the total orbital angular momentum of the electrons.
i

Useful references:

1. Bethe, H.A and Jackiw R; Intermediate Quantum Mechanics; West-view

press (1986).
2. Brandsen aB.H and joachain C.J; Physics of atoms and
molecules;Longman Group Limited (1983).
3. Landau L.D. and Lifshitz E.M; Quantum Mechanics Non-Relativistic
Theory; Pergamon Oxford (1977)