HF SCF

The Hartree-Fock Self-
Consistent-Field Method
Chem 561 – Fall 2009
Lecture Outline
1. The Hartree-Fock Energy (Levine 11.1)
a) Coulomb and exchange integrals
2. The Hartree-Fock Equations

a) The LCAO Approximation
3. The Hartree-Fock-Roothaan Equations
4. The Self-Consistent-Field Procedure (Levine 13.16)
5. Examples
a) H2+
b) He
HF SCF
the Hartree-Fock Self-Consistent-Field method
ab initio approach to solving the Schroedinger equation

for molecules
HF SCF
Recall the electronic Hamiltonian for molecules
Define
one-electron operator two-electron operator

HF SCF
No analytical solution to this differential equation
where
Use a trial-and-error, iterative approach

Molecular Hartree-Fock Wavefunction
a Slater determinant of one-electron spin orbitals (D)
spatial function spin function
the spin orbitals are an orthonormal set
Kronecker delta
Using the Variational Method
searching for a Slater determinant of spin orbitals (D)
that minimizes the variational integral
Since D is normalized
according to the previous definition

i and j label electrons
since the one-electron and two-electron operators do

not depend on spins
ui(1) is the ith spin orbital electron-nuclear attraction potential

occupied by electron 1 energy operator for electron 1
interacting with each nucleus
kinetic energy operator for electron 1

i and j label electrons
i labels spin orbitals
i and j label spin orbitals from Slater determinant
cross terms disappear because of orthonormality

Coulomb and Exchange Integrals
Define
Coulomb integral
Exchange integral
Coulomb and Exchange Integrals
for a closed-shell configuration of n electrons
half of the exchange integrals

disappear because of
orthonormality of spin functions
Hartree-Fock Energy
The Hartree-Fock energy is our best approximation to

the energy eigenvalue
Douglas Hartree
English mathematician and
physicist (1897-1958)
used numerical analysis to

solve differential equations
for the calculation of
atomic wavefunctions
the Hartree unit of energy is

named after him
Vladimir Aleksandrovich Fock
Soviet physicist (1898-1974)
introduced the exchange

term to the Hartree method
made significant
contributions to the general
theory of relativity
Hartree-Fock Energy
Coulombic (electrostatic)
Coulomb integral interaction between two electrons
Exchange integral A nonclassical interaction
Jij=Jji Kij=Kji Jii=Kii

Hartree-Fock Energy
Define
the one-electron core Hamiltonian
for a system of n electrons in n/2 occupied spin orbitals

The Hartree-Fock Equations
Back to the variational approach
Introduce linear variational parameters

a set of b variational
parameters
basis set functions

The spin orbitals are an orthonormal set
Since {csi} are also serving as normalization constants

for the basis set orbitals, they are not independent of
one another
To minimize a function subject to a constraint use
Lagrange multipliers
new function
Lagrange multiplier
Since the spin orbitals are an orthonormal set
Therefore as we minimize L we will also minimize EHF

We choose E such that
We are now ready to optimize with respect to each

variational parameter
We define
Fock operator
Coulomb operator
exchange operator
Using the Fock operator and the Lagrange multiplier
method
the Hartree-Fock equations
{εi} is a set of Lagrange multipliers
There is a Hartree-Fock equation for each electron in

the molecule
Significance of the variational parameters
Spin orbitals are expressed as a linear combination of
basis set orbitals
molecular orbitals atomic orbitals
LCAO-MO (linear combination of atomic orbitals)

introduced by Roothaan
not an approximation if the basis set is infinite
Example: bonding MO of H2
Clemens C.J. Roothaan
Dutch physicist (1918-)
Robert Mulliken’s student
moved to U.S. after WWII

Hartree-Fock-Roothaan Equations
Substitute the LCAO expansion in the set of Hartree
-Fock equations
Multiply both sides by χr* and integrate

Define
r and s number the a set of b simultaneous

basis set functions linear homogeneous
(1 to b) equations
Let’s expand Frs
Recall that
Therefore
Recall that
Therefore
Coulomb term
LCAO expansion of φj
Exchange term
LCAO expansion of φj
The Self-Consistent Field Method
the Hartree-Fock equations
Used to solve the Hartree-Fock-Roothaan equations
where
SCF Iterative Procedure
1. Given a basis set {χs} calculate

1. Given a basis set {χs} calculate

2. Make an initial guess at {cij}
3. Calculate
4. Solve the HFR equations to obtain {ει}
5. Use {εi} from previous step to obtain another set of csi
6. Use new {csi} to obtain new {εi}
7. Compare sets of energies: if not the same do another

cycle
Choose basis set Calculate Hrscore, Obtain set of cij

Srs, (rs|tu)
not the same
Solve HRF
Use {εi} to find
Calculate Frs equations to
new set of cij
find {εi}
Use cij’s to
Compare new
calculate new DONE
and old {εi}
{εi} same
EXAMPLES
H2+
2 2 2 2
− e' e' e'
Hˆ el = 2
∇1 − − ; VNN =
2me r1α r1β rαβ
molecular orbital (MO) Ψ = c1φ1 + c 2φ 2 + c n φ n trial wavefunction with linear variational

parameters
€
{φ
€i} is the basis set of atomic orbital (AO) functions
minimal basis set: valence atomic orbitals
H2+
H2+
Multiply by
H2+
Since
H2+
If we define
then
since
H2+
Similarly leads to
H2+
Compare to
These are Hartree-Fock-Roothaan equations!

b=2
Frs=Hrs because there is only 1 e-
H2+
Use SCF approach

Hij and Sij can be calculated since φ1s is known
To find the first value of <E>, we solve the secular
determinant
H2+
Since the basis set functions are normalized, SAA=SBB=1

H2+
Recall that HAB = HBA

H2+
The following integrals can be calculated exactly

H2+
Substitute HAA, HAB and SAB in the two homogeneous
linear equations
to find c1 and c2
H2+
The two wavefunctions are
bonding
antibonding
EXAMPLES
He Hartree-Fock-Roothaan
equations
minimal basis set: two 1s atomic orbitals
b=2 s=1,2 and r=1,2

He
He
2
H rscore = χ r − 12 ∇12 − χs
r1α
€
He
He
He
He
Summary
2
H11core = χ1 − 12 ∇12 − χ1
r1α
2
H12core = χ1 − 12 ∇12 − χ2
€ r1α
core 2
H 21 = χ 2 − 12 ∇12 − χ1
€ r1α
core 2
H 22 = χ 2 − 12 ∇12 − χ2
€ r1α
€
He
Choose the basis set
Calculate all integrals

S11=S22=1 S12=S21=0.8366
H11core = -1.8488 H12core = H21core =-1.8826 H22core = -1.5860
(11|11)=0.9062 (22|22)=1.8188
(11|22)=(22|11)=1.1826
(12|12)=(21|12)=(21|21)=0.9536
(11|12)=(11|21)=(12|11)=(21|11)=0.9033
(12|22)=(22|12)=(21|22)=(22|21)=1.2980
He
Initial guess: c11=0.6922 and c21=0.3461
Solve the secular determinant
Find ε1 and ε2
Substitute ε1 in the HFR equations above to find the new values

of c11 and c12
repeat until self consistency is achieved

HF SCF

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The Hartree-Fock Self-

2. The Hartree-Fock Equations

3. The Hartree-Fock-Roothaan Equations

4. The Self-Consistent-Field Procedure (Levine 13.16)

ab initio approach to solving the Schroedinger equation

one-electron operator two-electron operator

Use a trial-and-error, iterative approach

a Slater determinant of one-electron spin orbitals (D)

spatial function spin function

the spin orbitals are an orthonormal set

according to the previous definition

i and j label electrons

since the one-electron and two-electron operators do

ui(1) is the ith spin orbital electron-nuclear attraction potential

kinetic energy operator for electron 1

i labels spin orbitals

i and j label spin orbitals from Slater determinant

cross terms disappear because of orthonormality

for a closed-shell configuration of n electrons

half of the exchange integrals

The Hartree-Fock energy is our best approximation to

used numerical analysis to

the Hartree unit of energy is

introduced the exchange

Exchange integral A nonclassical interaction

Jij=Jji Kij=Kji Jii=Kii

for a system of n electrons in n/2 occupied spin orbitals

Introduce linear variational parameters

basis set functions

The spin orbitals are an orthonormal set

Since {csi} are also serving as normalization constants

Therefore as we minimize L we will also minimize EHF

We are now ready to optimize with respect to each

the Hartree-Fock equations

{εi} is a set of Lagrange multipliers

There is a Hartree-Fock equation for each electron in

molecular orbitals atomic orbitals

LCAO-MO (linear combination of atomic orbitals)

Robert Mulliken’s student

moved to U.S. after WWII

Multiply both sides by χr* and integrate

r and s number the a set of b simultaneous

Used to solve the Hartree-Fock-Roothaan equations

1. Given a basis set {χs} calculate

1. Given a basis set {χs} calculate

2. Make an initial guess at {cij}

5. Use {εi} from previous step to obtain another set of csi

6. Use new {csi} to obtain new {εi}

7. Compare sets of energies: if not the same do another

Choose basis set Calculate Hrscore, Obtain set of cij

not the same

molecular orbital (MO) Ψ = c1φ1 + c 2φ 2 + c n φ n trial wavefunction with linear variational

These are Hartree-Fock-Roothaan equations!

Use SCF approach

Since the basis set functions are normalized, SAA=SBB=1

Recall that HAB = HBA

The following integrals can be calculated exactly

minimal basis set: two 1s atomic orbitals

b=2 s=1,2 and r=1,2

Choose the basis set