AB INITIO MOLECULAR ORBITAL

Definition
The term ab initio means from first
principles. It does not mean that we are
solving the Schrdinger equation exactly.
It means that we are selecting a method that
in principle can lead to a reasonable
approximation to the solution of the
Schrdinger equation and then selecting a
basis set that will implement that method in a
reasonable way.
Hartree-Fock method
The essential idea of the Hartree-Fock or
molecular orbital method is that, for a closed
shell system, the electrons are assigned two
at a time to a set of molecular orbitals.

{ } ) 8 ( ) 8 ( ) 7 ( ) 7 ( ) 6 ( ) 6 ( ) 5 ( ) 5 ( ) 4 ( ) 4 ( ) 3 ( ) 3 ( ) 2 ( ) 2 ( ) 1 ( ) 1 ( det
4 4 3 3 2 2 1 1
| | o | | | o | | | o | | | o | =
Here each molecular orbital
i
is now expanded as
a linear combination of basis functions, |

Our aim is to find the value of the coefficients C
i

that gives the best molecular orbitals. The sum is
over n basis functions. n is the number of basis
functions chosen for the system.

=
=
n
i
C
1

|
We expand each molecular orbital in terms
of a set of basis functions which are normally
centred on the atoms in the molecule.
Basis of M.O. Theory...
Three Simplifying assumptions are employed to solve the
Schrdinger equation approximately:
Born-Oppenheimer approximation allows separate
treatment of nuclei and electrons
Hartree-Fock independent electron approximation allows
each electron to be considered as being affected by the
sum (field) of all other electrons.
LCAO Approximation
Variational Principle

Schrdinger equation
The energy of an isolated molecule can be obtained by the solution of the
Schrdinger equation. In its time-independent form
is the Hamiltonian operator, is the wave function, and E is the energy of
the system
H

E H =

Hamiltonian Operator
The Hamiltonian contains one- and two-electron terms. The two-
electron terms (summed over i and j) are just the repulsion potential
energies between all pairs of electrons.

1/rij is the repulsion between a pair of electrons (distance rij apart).

+ =
i j
ij
i
i
r
h H
1

The one-electron terms (summed over i) are

more varied. For each electron, there is a kinetic
energy term and a sum of attractive potential
energy terms for each nucleus in the molecule.
-1/2 V
i
2
is the kinetic energy term
Z
A
/r
Ai
is the coulombic attraction between
electron i and nucleus A.
Z
A
is the nuclear charge (atomic number) of
atom A and r
Ai
is the distance between
electron i and nucleus A.

2
1
2
2
2
2
2
2
2 2
i i i
z y x
i
A
Ai
A
i i
r
Z
h
c
c
+
c
c
+
c
c
= V V =

Born-Oppenheimer Approx.
States that electron motion is independent of nuclear motion,
thus the energies of the two are uncoupled and can be
calculated separately.
Derives from the large difference in the mass of nuclei and
electrons, and the assumption that the motion of nuclei can
be ignored because they move very slowly compared to
electrons
H
tot
a (T
n
) + T
e
+ V
ne
+ V
n
+ V
e
Kinetic energy Potential energy
(T
n
is omitted; this ignores relativistic effects, yielding the
electronic Schrdinger equation.)
Hartree-Fock Approximation
Assumes that each electron experiences all the others only as
a whole (field of charge) rather than individual electron-
electron interactions.

Introduces a Fock operator F:
F
which is the sum of the kinetic energy of an electron, a
potential that one electron would experience for a fixed
nucleus, and an average of the effects of the other electrons.


Born-Oppenheimer approximation
The masses of the nuclei are much larger and
their velocities much smaller than those of the
electrons.
The Schrdinger equation by separating it into
two parts, one describing the motions of the
electrons in a field of fixed nuclei and the other
describing the motions of the nuclei.
The electronic Schrdinger equation:
el el el el
E H =

The orbital approximation

The orbital approximation assume that each
electron is associated with a separate one-
electron wavefunction or spin orbital
Hartree proposed that the wavefunction could
be expressed simply as a product of spin
orbitals, one for each electron:
= _
1
(1) _
2
(2) .... n(n)
The LCAO approximation
Each spin orbital is actually a product of a
spatial function,
i
(x,y,z), and a spin
function, |
a
or |
b
. The spatial molecular
orbitals,
i
, are usually expressed as linear
combinations of a finite set of known one-
electron functions.
This expansion is called a linear combination of
atomic orbitals (LCAO)
N Ni i i i
c c c | | | + + + = ...
2 2 1 1
LCAO Approximation
Electron positions in molecular orbitals can be approximated by a
Linear Combination of Atomic Orbitals.
This reduces the problem of finding the best functional form for the
molecular orbitals to the much simpler one of optimizing a set of
coefficients (c
n
) in a linear equation:
= c
1
f
1
+ c
2
f
2
+ c
3
f
3
+ c
4
f
4
+

where is the molecular orbital wavefunction and f
n
represent
atomic orbital wavefunctions.
Variational Principle
The energy calculated from any approximation of the
wavefunction will be higher than the true energy.
The better the wavefunction, the lower the energy (the more
closely it approximates reality).
Changes are made systematically to minimize the calculated
energy.
At the energy minimum (which approximates the true energy of
the system), dE
calc-real
~ 0.
Basis sets
A basis set is a set of mathematical equations used to
represent the shapes of spaces (orbitals) occupied by
the electrons and their energies.
Basis sets in common use have a simple mathematical
form for representing the radial distribution of electron
density.
Most commonly used are Gaussian type basis sets, which
approximate the better, but more complicated Slater-
Type orbitals (STO).

Slater-type orbitals (STO)
Slater-type orbitals describe the
electron distribution quite well,
but they are not simple enough
to manipulate mathematically.
Several Gaussian-type orbitals
can be added together to
approximate the STO. Here 4
GTOs mimic 1 STO fairly well.
Basis Sets
STO-3G (Slater-type orbitals approximated by 3 Gaussian
functions) a minimal basis set, commonly used in Semi-
Empirical MO calculations.
Derivation of the 2-electron secular
equation
The energy is calculated by taking into account
the interaction of each electron with the
average field of all the other electrons. For
each electron i, the Schrdinger equation may
be written as:

i i i
f c =
f is the one-electron Fock operator which
includes kinetic and potential energy terms
of one electron in the average field of the
others.
LCAO approximation for
i
:
u
u

c
| | c | |
u u


} } }

=
=
S C F C
C C
i i i
i i i
* *
Multiplying both sides by |
u
* and integrating gives
F is called the Fock matrix and
S is called the overlap matrix
the c
i
(the eigenvalues) represent the energies of the
orbitals i,
the Ci (the eigenvectors) represent the molecular
orbitals coefficients of i.

=
n
i i
C

|

= =
=
N
i i
N
i
C C f
1 1

| c |
i i i
SC FC c =
Self-Consistent-Field (SCF) theory
Fock matrix itself depends on the coefficients
Ci and therefore it is necessary to use an
iterative procedure when solving the
equation.
We guess values for the Ci initially and the
variational principal (which states that E
guess
is
always > E
true
) allows us to optimise the C
i

until we reach self consistency
Electron configuration
Close-shell system-all electrons are paired
Open-shell system - to pair up as many electrons
as possible
A system containing unpaired electrons (eg
radicals, biradicals, etc).
ROHF: Restricted Open Shell Hartree-Fock
method
UHF: Unrestricted Hartree-Fock
The alpha and beta molecular orbitals are not
constrained to have the same molecular
orbital coefficients.
multiplicity = 2S + 1
S = the number of unpaired electrons x 1/2
Outline of a calculation
Read input & calculate a geometry
Assign basis set
Calculate nuclear repulsion energy
Calculate integrals
Assign electronic configuration
Generate initial guess
Perform self-consistent field iterations (i.e.
calculate the electronic energy)
Calculate total energy = nuclear repulsion +
electronic
Perform electron density analysis
Carry out further steps...

Assumptions of ab initio quantum
chemistry
Assume that the Born-Oppenheimer
approximation holds (ie. that the nuclei
remain fixed on the scale of electron
movement). This assumption can become
invalid when two electronic states lie very
close together.
Assume that basis sets adequately represent
molecular orbitals.
Assume that electron correlation is
adequately included within a certain level of
theory
Capabilities of ab initio quantum chemistry
Can calculate the geometries and energies of
equilibrium structures, transition structures,
intermediates, and neutral and charged species
Can calculate ground and excited states
Can handle any electron configuration
Can handle any element
Can calculate wavefunctions and detailed
descriptions of molecular orbitals
Can calculate atomic charges, dipole moments,
multipole moments, polarisabilities, etc.
Can calculate vibrational frequencies, IR and Raman
intensities, NMR chemical shifts
Can calculate ionisation energies and electron
affinities
Can include the electrostatic effects on solvation
Limitations, strengths & reliability of ab
initio quantum chemistry
Limitations
Requires more cpu time than empirical or semi-empirical methods
Can treat smaller molecules than empirical and semi-empirical
methods
Calculations are more complex
Have to worry about electronic configuration

Strengths
No experimental bias
Can improve a calculation in a logical manner (basis sets, level of
theory)
Provides information on intermediate species, including
spectroscopic data
Can calculate novel structures (no experimental data is required)
Can calculate any electronic state