STiAP Self Assessment 3

Department of Physics PCD_STiAP_Self_Assesment_3
IIT-Madras 20 marks
1. Write down the Hamiltonian for the N electron system. Describe each term in the
Hamiltonian. -2 marks
N
 1 Z N 1
A1. H ( N )     i 2     m;  1
i 1  2 ri  i  j 1 rij
Kinetic energy term

Potential energy term of each electron in the field of Z nucleus.
Coulomb repulsion between every pair of electrons.
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2. What is the principle followed in Hartree Fock formalism to attain the self consistency?
What are the constraints the method is subjected to? -2 marks
A2. The Variational principle is used in Hartree Fock formalism to attain self-consistency.
The Constraints are
(i) Normalization of the spin orbitals ui u j  1 for j  i
(ii) The orthogonality ui u j  0 for j  i
Where i, j stand respectively for the Collective Complete set of good Quantum numbers
n, l , ml , ms of the ith and jth occupied single-particle states.
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3. In the given wave function equation of N electron system what is Â and how it is
expressed. Explain the operator. – 3 marks
 ( N ) (q ,.., q )  A ˆ u (q )u (q )..u (q )
1,2,... N 1 N 1 1 2 2 N N
1 N! 1
Â is the Antisymmetriser operator expressed as 
N ! P 1
(1) p P .
N!
is the normalization
factor. There are N ! ways of permuting the N indistinguishable electrons in the N quantum
states. For every permutation there will be a sign change which is represented by (1) p and
since there is N! ways the summation of P going from 1 to N!. The operator takes the
direct product of the diagonal element from the Slater Determinant and antisymmetrise it.
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4. Write down the wave function for a two electron system in the form of Slater determinant
and explain the terms in each rows and columns. What are the principles included in Slater
determinant form.
-3 marks
(q1 , q2 )  N u1 (q1 )u2 (q2 )  u1 (q2 )u2 (q1 )

ui (q j )   j | i   rj ,  j | ni , li , mli , msi 
ui (q j )   rj | ni , li , mli   j | msi 
 rj | ni , li , mli  is the space part ;  j | msi  is the spin part
 (q1 , q2 )  N u1 (q1 )u2 (q2 )  u1 (q2 )u2 (q1 ) 
1 u1 (q1 ) u1 (q2 )

2 u2 (q1 ) u2 (q2 )
Rows: occupied of single particle states (labelled by a set of 4 quantum numbers) in the
many-electron system
Columns: set of (space, spin) coordinates
The principles included in the Slater determinant form are 1) Pauli’s exclusion Principle 2)
Antisymmetry of the wavefunction
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5. Consider 2-electron wavefunction  (q1 , q2 )   (r1 , r 2 )  ( 1 ,  2 ) made up as an
antisymmetrized product of 1-electron spin-orbitals ni ,li ,ml (r j )  ms ( j ) . – 1+2+2 marks
i i
a. What are the states corresponding to S  0 and S  0,1 . How are they represented?
b. Write the form of the wavefunction for Singlet and Triplet state.
c. Which state has lower energy? What factor determines the energy of the state?
A5.a. The State corresponding to S=0 is Singlet state and S=0, 1 is Triple state
Consider a two electron system with coordinates q1 and q2. If the electrons are
interchanged, the wave functions are given by in terms of spatial and spin part,
 (q1 , q2 )   (r1 , r 2 )  ( 1 ,  2 )

 (q2 , q1 )   (q1 , q2 )    (r , r )  ( 1,  2 )
1 2 
 
 (q2 , q1 )   (r , r )  ( 1 ,  2 )
1 2
  (r 1 , r 2 )   ( 1 ,  2 )
Either the spatial part should be antisymmetric corresponding to Triplet state or the spin
part should be antisymmetric corresponding to Single state.
b.  (r 2 , r 1 )   (r 1 , r 2 )  N 1 (r 1 )2 (r 2 ) +1 (r 2 )2 (r 1 )  antisymmetric spin part –

Singlet state
 (r 2 , r 1 )   (r 1 , r 2 )  N 1 (r 1 )2 (r 2 )  1 (r 2 )2 (r 1 )  antisymmetric spatial part –
Triplet state
c. The triplet state has lower energy when compared to Singlet state. In above equation, If
r1 tends to r2 the triplet state vanishes. For the triplet state to exist the distance between 2
electrons r12 should be large so that the columbic repulsion force 1/r12 reduces. Thus the triplet
states have lower energy.
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6. True or false. – 4 marks
a. Exchange correlations are included in Hartree formalism. – False
b. Coulomb correlations are included in Hartree Fock formalism. – False
c. For, exchange term to exist, we should have an overlap between the spatial parts. – True
d. Exchange correlations are also called as Fermi Dirac statistical correlation. – True
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7. What is the physical significance of Lagrange multipliers – 1 mark
It represents the ionization energy of that particular orbital from which the electron is
removed.
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Department of Physics PCD_STiAP_Self_Assesment_3

Kinetic energy term

(q1 , q2 )  N u1 (q1 )u2 (q2 )  u1 (q2 )u2 (q1 )

b.  (r 2 , r 1 )   (r 1 , r 2 )  N 1 (r 1 )2 (r 2 ) +1 (r 2 )2 (r 1 )  antisymmetric spin part –

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