Hartree-Fock

Hartree-Fock
Nama metode ini diambil dari nama :
Douglas Hartree yaitu ilmuwan yang menemukan
metode self consistent field, dan
V. A. Fock yang menunjukkan ketepatan logika
metode Hartree dan merumuskannya kembali
menjadi bentuk matriks yang digunakan sekarang.
 Metode Hartree-Fock
• Fungsi gelombang atom merupakan perkalian dari fungsi
gelombang tiap-tiap elektron :
 r 1,r 2,r 3...r N = 1 r 1 2 r 2 3 r 3 ...N r N
Untuk molekul  Koreksi Fock dan Slater (Prinsip Pauli)

• Hampiran Born-Oppenheimer
Penyelesaian persamaan Schrodinger untuk elektron-elektron
dalam medan inti statis.
• Penggantian many-electrons Hamiltonian dengan an effective
one-electron Hamiltonian
 Limitations of the Hartree approximation
The Hartree approximation works well for atoms. However,
the form of the wave function is not correct and the method
fails for molecules. One property of the wave function is
that is must change sign when any two electrons are
interchanged. Around 1930 both Fock and Slater proposed
to fix the problem with Hartree model by introducing a
wave function that is anti-symmetric with respect to electron
exchange
1 r 1 2 r 1 3 r 1 ...N r 1
1 r 2 2 r 2 3 r 2 ...N r 2
1 r 3 2 r 3 3 r 3 ...N r 3
 r 1,r 2,r 3,...r N = 1 .
.
N! .
1 r N 2 r N 3 r N ...N r N

The wave function is the determinant of the matrix.

 Pauli Principle

• Anti simetry :
• Exclusion Principle :
Hamiltonian (Ĥ)
Merupakan operator energi total dari sistem (atom atau molekul), yaitu
jumlah energi kinetik dan potensial total :

Contoh: atom He
2
2
e
U ee  r
– h  12 - 12
2
2m – h  22
2
- 2m
– Ze
r1
++
2
Ze
– r
2
Pendekatan Born-Oppenheimer
Inti jauh lebih berat dari pada elektron
me = 9.109x 10– 31 kg
mp = 1.672x 10– 27 kg
akibatnya inti dapat dianggap statis, dengan elektron
bergerak sangat cepat disekitarnya. Dalam kasus ini
pergerakan elektron dan inti dipisahkan sehingga
Hamiltonian menjadi :

H el = Te + Vext + U ee
 The nuclear hamiltonian
The Born-Oppenheimer approximation states that electronic
and nuclear motion can be separated because of the large
difference in mass (1 proton has 1836 times the mass of an
electron). Thus, the nuclear kinetic energy and repulsion terms
are not included. However, it is important to understand that
the nuclear terms are used for translational, rotational and
vibrational motion. Vibrations are of particular relevance since
the quantum chemical calculation of vibrational frequencies
is the basis for parameterization of classical molecular force
fields.
Tnucl = – 
2
h  2j Kinetic energy term
j 2M j

Z je 2
Unucl =  Nuclear repulsion energy
j Rj
 The effective hamiltonian
Using these approximations we can write the hamiltonian
of an atom as
H el = Te + Vext + U ee

The first two terms alone comprise a set of N hydrogen

atom calculations which can be solved exactly.

Te + Vext = – i i i
h 2  2 + Ze 2 = h
2m i ri

The total hamiltonian in this nomenclature is:

H el = i h i + U ee
Note that the inclusion of the electron-electron repulsion
term Uee makes it impossible to solve the Schrodinger
equation using this hamiltonian.
 Hartree Approximation
The kth electron is now treated as a point charge in the
field of all of the other electrons. This procedure takes
the many-electron problem and simplifies it to many
one electron problems.

-
-
-
-
+ +
-
-

One-electron system
Many-electron system
with remaining electrons
All electron-electron repulsion
represented by an average
is included explicitly.
charge density.
 The Hartree approximation
The method is to solve the Schrodinger equation for each
individual electron in the field of all of the other electrons.
If we assume that we know the individual wave functions
φi(r) for each electron we can calculate the electron density
according to:
 i = |i r |
2

The total electron density is:

 tot = i  i = i |i r |
N N
2

However, the kth electron does not interact with itself so

Must subtract the density of rk from the total.

  i – | r | = i
N N
 =  tot –  k =
2 2
(k)
k |i r |
i =1
ik
 The Hartree procedure
The interaction of the point charge with the electron
density is
gk r =  (k) r 1 dr
|r – r|
Making this approximation we can write

U ee  i g i r
N

and the hamiltonian Hel now consists of one-electron

operators:
H el  i h i + g i
N

The many-electron Schrodinger equation can now be

Solved as N one-electron Schrodinger equations


N

i
h i + g i i =  ii
 The Coulomb integral
The set of one-electron Schrodinger equations can be
solved iteratively to find the best energy. According to
the variational principle the true energy will always be
lower than the energy calculated using this method.
However, this method counts the interacion between each
pair of electrons twice. Therefore, we cannot simply add
the individual one-electron energies εi to obtain the total
energy E. We correct for this using the Coulomb integral
between each pair of electrons Jij such that

E = i  
N N–1 N

=1
i + i=1 j=i+1
J ij
The Coulomb interaction between each pair of electrons is
 i r1  j r2
J ij = dr 1dr 2
|r 2 – r 1|
 The exchange integral
The new determinantal wave function adds a new term to
the Hartree energy, the exchange term Kij.

E = i 2 i 
N N N

=1
 i + 1
=1 j=1
J ij – K ij

We compare the Coulomb and exchange integrals below.

J ij = i* r 1 i r 1 1  * r  r dr dr
|r 2 – r 1| j 2 j 2 1 2
K ij = i* r 1  j r 1 1  r  r dr dr
|r 2 – r 1| i 2 j 2 1 2

Notice that the difference is a rather subtle swap of the

indices i and j. This small change has a profound effect
on the contribution calculated by the integral.
 The Fock equations
The procedure leads to the Fock equations.
f r 1 i r 1 =  ii r 1

The Fock operator is a one-electron operator

f r1 = h r1 + 
N

a
ja r 1 – k a r 1
The choice of electron 1 is arbitrary. These equations
can written for all of the electrons. The Coulomb and
exchange terms are
ja r 1 b* r 1 = b* r 1 |a r2 |
2 1 dr
|r 2 – r 1| 2
k a r 1 b* r 1 = a r 1 a* r 2 b r 2 1 dr
|r 2 – r 1| 2
 Matrix representation
The fock hamiltonian is an effective one-electron hamiltonian
H eff i = Eii H eff  f r

AOs: { 1,  2,  3, ...., N }

C
N
MOs: i = ii
=1

The matrix representation for the overlap and interaction

energies is:

S 11 S 12 S 13 ...S 1N H 11 H 12 H 13 ...H 1N C1i

S 21 S 22 S 23 ...S 2N H H 22 H 23 ...H 2N C
S = ... ... ... ... H = ... 21
... ... ... Ci = ...2i
S N1 S N2 S N3 ...S NN H N1 H N2 H N3 ...H NN C Ni
 Matrix representation
Thus, HCi = EiSCi
Define the matrices of coefficients and eigenvalues as:

C11 C12 C13 ...C1N E11 0 0 ... 0

C21 C22 C23 ...C2N 0 E22 0 ... 0
C = ... ... ... ... , E = ... ... ... ...
C N1 C N2 C N3 ...C NN 0 0 0 ... E NN

Then the matrix form is HC = SCE. This system of equations

is diagonalized if det|H - ES| = 0. However, this is possible
only in the MO basis.
AO basis: { 1,  2,  3, ...., N } MO basis: {1, 2, 3, ....,N }
S  = < | > : Not orthogonal  ij = <i| j> : Orthogonal
H  = < |H eff | > : Not diagonal Ei ij = <i|H eff | j> : Diagonal
 Eigenvalues are energies and
eigenvectors are MOs
The procedure is carried out until a self-consistent
minimum energy is found. The resulting self-consistent
field (SCF) energy is the Hartree-Fock procedure.

The values for the coefficients that give the SCF

energies for the electronic states give the MOs. As
shown previously we can think of these as linear
combinations of atomic orbitals.

The linear combinations have distinctive shapes such

as those shown for the MOs of N2 in the following.
Procedure for Solving the Hartree-Fock Equation
1) Choose a trial function φ. This will usually be a product or linear
combination of hydrogen-like orbitals.
2) Calculate V1eff with the trial function.
3) Calculate a new φ by solving the radial equation.
4) Compare the old and new φ's.
5) If the new orbital wavefunction is different from the old, we take the
new orbital φ, calculate a new V1eff and repeat the process until at step
four there is no discernible difference between the old and new
orbitals.
At this point the calculation is finished, the initial and final orbitals
areconsistent with each other, and for this reason, this method of
solving the Hartree-Fock equation is called the self-consistent field
method.
 Hartree-Fock is not well suited to
calculation of excited state properties
Hartree-Fock theory works well for ground state
properties because the energies of occupied
orbitals are relatively accurately determined.
However, the energy of unoccupied orbitals is not
well determined and therefore excited state
properties and transition energies are not well
determined within the HF approach. To account
for excited state properties one can include
excited electron configurations. Such ab initio
approaches that move beyond HF theory are
collectively called configuration interaction (CI).
 Summary of Hartree-Fock
Method
• Assumes a single Slater-determinant for the electronic
wavefunction, which satisfies the Pauli Principle of many-
electron systems
• and variationally optimizes the MOs by minimizing the exact
energy expression for the Slater-determinant wavefunction
under the orthonormality condition of the MOs.
• The electronic energy is expressed by one-electron integrals
Heff and Coulomb and Exchange two-electron integrals Jij and
Kij.