Ab initio Methods

Ab initio Methods
Lopez Sosa Luis & Tenorio Barajas A.Yair
Departamento de Qumica
CINVESTAV
Computational Chemistry
PhD. Andreas M. Kster

Ab initio Methods
Introduction
Content

Ab initio what means?

Common uses
Hartree Fock Method
Variational principle
Slater determinant
Linear Combination of Atomic Orbitals
Post Hartree Fock Methods
Electronic Correlation
Configuration Interaction
Perturbation Theory
Mller-Plesset Perturbation Theory
Coupled Cluster Method
Some results in calculations
Advantages and Disadvantages
Conclusions

Ab initio Methods
Introduction

The term Ab initio from its latin form means "from the beginning".
This name is given to the computations that are derived directly
from theoretical principles with no inclusion of experimental data.
An Ab initio calculation use the most fundamental physical
quantities and only enters a value for a trial wave function.
Ab initio methods use the correct Hamiltonian

Ab initio Methods
Introduction
Common Uses

Common Uses
Calculating:
Molecular geometries
Energies
Vibrational frequencies
Spectra
Ionization potentials and
Electron affinities.

Ab initio Methods
Introduction
Authors

Hartree-Fock

Douglas Rayner Hartree

Vladmir Aleksndrovich Fock

William Hartree

Bertha Swirles

Ab initio Methods
An Example He

The Hartree Fock Method for He

First we will write the two-electron wave function as product
of orbitals, this is the Hartree product.

(r1,r2 ) = (r1)(r2 )

(1)

Functions (r1) and (r2 ) are equal, and we can write the
potential energy due electron repulsion like:
V (r1) =
eff
1

1
(r2 ) (r2 )dr2
r12
*

(2)

The Hamiltonian over (r1) can be expressed like:

eff
1 2 2
!
H1 (r1) = 1 + V1eff (r1)
2
r1

And the effective Hamiltonian for He:

eff
!
H (r )(r ) = (r )
1

(3)
(4)

Ab initio Methods
An Example He
eff
!
H1 (r1)

Here
depends from (r2 ) and this is a pseudo eigenvalue
equation to solve it we need the method self consistent field
SCF and is found in the variational principle
SCF Method follow the next steps

Guess a value for (r2 )

eff
V
Evaluate potential energy for repulsion 1 (r1)
Solve Hartree Fock equation to obtain (r1)
eff
V
Evaluate again 1 (r1) but using (r1)
Solve HF equation to obtain again (r1)
And so on until the difference between the value obtained and
the value introduced reach an acceptable value

Ab initio Methods
An Example He

One calculation for He with Hartree Fock is EHF =-2.862Eh,

compared with the Eexact= -2.903Eh
The difference in values is due to the fact that both electrons
are considered not interacting with each other, or an average
interaction
Electrons are uncorrelated, and the correlation energy is:
CE=Eexact - EHF
For this case, CE= -110kJ/mol this is the energy for a chemical
bond and thus is not enough precise

Ab initio Methods
Variational Principle

Variational Principle
Schrdinger equation can be solved exactly only for H atom but
we can solve it for other atoms approximately and a very good
approach is performed by the variational principle
If 0 is the ground state wave function of a system, then the
approximate function , is such that:
E E 0

(5)

!
H0 = E0 0

(6)

Consider a system with a fundamental state as the wave function 0

with a solution with the Schrdinger equation E0 with eigenvalue

we can write:
E0

! d
0* H
0

=
d
*
0

(7)

Ab initio Methods
Variational Principle

Substituting other function instead of 0 in equation (7)

E0

! d
0* H
0

*
0 0

(8)

But according with the variational principle

E E0

So equality in energy only happen if = 0

If our trial wave function depends on parameters ,,,...,
variational parameters the energy is going to depend on this
parameters as well
(9)
E (,,,...) E0
!And we can minimize the energy varying this parameters
dE (i)
di

= 0 with i = ,,, . . .

an obtain the best parameters for the trial wave function

10

Ab initio Methods
Slater Determinant

Slater Determinant
The wave function must be antisymmetric due the nature of the
electron so (i, j) = ( j,i) and be in agreement with Pauli exclusion
principle
mathematically this can be done with a determinant
1(1)
(1,2,...n) =

2 (1)

...

n (1)

1(2) 2 (2) ... n (2)

n!

...
...
...
1(n) 2 (n) ... n (n)

(10)
John C. Slater

This Slater determinant is built with molecular orbitals whit i

indexing the electron and j the orbital were the electron i is j (i)
! Exercice
11

Ab initio Methods
LCAO

In molecular orbital theory orbitals inside Slater determinant are

molecular orbitals
A systematic construction of this MO is achieved with the linear
combination of atomic orbitals abbreviated LCAO
(11)
i (r ) = Ci (r )

This expansion will be used in calculation of the so called core

Hamiltonian
The electronic Hamiltonian operator for a N electronic molecule
with atomic nuclei A is
n
ZA
1 2
1
!
H = i
+
2
i
A,i rA,i
i>k ri,k

(12)

Defining the core Hamiltonian operator for kinetic and potential

energy of one electron like:
ZA
1 2
!
h(i) = i
2
A rAi
12

(13)

Ab initio Methods
Hartree Fock Method

The Coulomb operator involves electrostatic repulsion between

electrons, this term is:
!j(a,b) = 1
(14)
r r
a

Originally the core Hamiltonian acts over spin orbitals but this can
be changed for spatial orbitals thanks to the model of independent
particles
(15)
j (i) j (r, i ) = j (ri ) j (i )
So we can write the expectation value of the core Hamiltonian with
the 2 counting for two electrons in each orbital
occ

!
h = 2 i !
h i

(16)

Similarly the expectation value for Coulomb operator is:

1
!

j = 2 i i j j i j j i

2
1
j
occ

occ

13

(17)

Ab initio Methods
Hartree Fock Method

The Coulomb integral represents the repulsion experienced by

electron 1 in orbital i from electron 2 2 in orbital j where it is
distributed with probability density and there are 2 electrons in
each orbital, so we can expect a total contribution of the form
!J(1,2) =

i (1)i (1) j (2)*j (2)

dr1dr2
r1 r2

(18)

The exchange integral is a correction to the Coulomb integral due to

the fact that exist an error when i=j
E

!
K(1,2) =

2
2

i (1)*j (1) j (2)i* (2)

dr1dr2
r1 r2

j
i
14

(19)

Ab initio Methods
Hartree Fock Method

Taking the order of the Hamiltonian elements H=Ke+Ven+Vee+Vnn

core Hamiltonian + Coulomb operator + exchange operator
occ

E = 2
i

occ occ
1
!
i h i + 2 i i ! j j i j ! i j

2
i
j

(20)

or
n

E = 2 Hi,i + 2 2 Ji, j K i, j

i
i
j

(21)

This is the Hartree Fock closed-shell energy and only the value for
the trial function is introduced, this is restricted to a single
determinant and thus, correlation between electrons of oposite spin is
neglected. This problem is treaty by post Hartree-Fock methods.

15

Ab initio Methods
Roothaan-Hall equations

The key to make MO calculations feasible was proposed by

Roothaan and Hall in 1951, He express the MO as a linear
combination of basis functions set of one electron LCAO.

i (r ) = Ci (r ) (11)

Clemens C. J. Roothaan

George G. Hall

To represent correctly the MO the basis function must be form a

complete set and this require an infinite number of basis functions,
in practice if we chose a big enough number for mu, and correct
functions, we can represent MO with a negligible error.

16

Ab initio Methods
Roothaan-Hall equations

If we use the LCAO and introducing this expansion in the core

Hamiltonian we obtain
occ

!
!
h = 2 C,i Ci h

(22)

Here the core Hamiltonian matrix elements !h are defined over

atomic orbitals mu and nu instead of molecular orbitals
To simplify we introduce now the closed shell density matrix
occ

P = 2 C,i Ci

And the above equation leads us:

!
h = P !
h
,

17

(23)
(24)

Ab initio Methods
Roothaan-Hall equations

If we use the LCAO and introducing this expansion in the Coulomb

operator in a similar way we obtain, and molecular orbital integrals
are reduced to additions of integrals over atomic orbitals

1
!
j = 2 Ci Ci C j C j

2
i, j , ,

occ

(25)

Atomic orbitals form the basis for MO theory calculus and are
called basis set
This basis set and geometry is the essential input for calculations in
MO theory
Expansion coefficients Ci are the MO coefficients, and are the
values we are searching for and we will try to find it in our
calculations.

18

Ab initio Methods
Roothaan-Hall equations

Putting together the core Hamiltonian and the Coulomb operator

with the core Hamiltonian matrix elements !h = H we have:

1
E = 2 C,i Ci H + 2 Ci Ci C j C j

2
i
,
i, j , ,

occ

occ

(26)

This is the expression for Hartree-Fock energy with the

approximation of LCAO
The HF equations are derived from the premise that we need to find
out the best coefficients in eq. (26) in order to minimize the E, and
we need to take into account the restriction of orthonormality
of MO

i j = Ci S C j = i, j
,

S represent an element of the overlap matrix

19

(27)

Ab initio Methods
Roothaan-Hall equations

Is convenient to write eq (27) in matrix form. To work with quadratic

matrices of same dimensions all atomic and molecular orbitals are
taken into account

Fc = Sc

(28)

This is the Roothaan-Hall equation system. F is the Fock matrix, c is

the MO coefficient matrix, S the overlap matrix and lambda the
Lagrange multiplier matrix.

20

Ab initio Methods
Roothaan-Hall equations

Simplifying by diagonalization of Lagrange multiplier matrix

U = U

(29)

with as diagonal matrix with eigenvalues of ,and U is an

orthogonal unitary transformation matrix with properties:
t
t
(30)
UU = U U = I
where I is the unit matrix
inserting = UU t into Fc = Sc and multiplying by U

FcU = ScU

(31)

if canonical MO coefficients are introduced where

*

c = cU

(32)

the Roothaan-Hall equation can be written in its canonical form

*

Fc = Sc
21

(33)

Ab initio Methods
General procedure

SCF Hartree-Fock,Roothaan-Hall flow path

Calculation of MO integrals

Calculation of start density

Calculation of HF matrix
Minimization of energy
by diagonalization of HF matrix
Calculation of new density matrix
Calculation of SCF energy

No

Consistent energy?
SCF

22

Yes

Total energy

Ab initio Methods

Post-Hartree Fock
Methods

23

Ab initio Methods
Post HF
Electronic Correlation

Electronic Correlation
The interaction between electrons in a quantum system is known
as electronic correlation.
We have seen approximation solutions to the real wave function.
Hence, based on the variational principle, the energy computed
will be higher than the ground state energy.

24

Ab initio Methods
Post HF
Electronic Correlation

The difference between these two energies is known as the

correlation energy (Eq. 35).

(34)

(35)

25

Ab initio Methods
Post HF

Hence, the final step in improving MO calculations is to recover

some of this correlation energy. These methods can be classified
as:
1) Wave function-based methods:
Configuration interaction (CI)
The Mller-Plesset perturbation theory (MP)
Coupled cluster (CC)
2) Electron density based methods:
Density functional theory (DFT)

26

Ab initio Methods
Post HF
Configuration Interaction

Configuration Interaction (CI)

We

start with a trial wave-function, which is written as a linear

combination of determinants with
expansion coefficients
based on the variational principle.

(36)

27

Ab initio Methods
Post HF
Configuration Interaction

The Configuration Interaction treatment for electron

correlation is based on the idea that one can improve on the
HF wave-function, and therefore the energy, adding terms into
HF wave-function represents promotion of electrons from
occupied to virtual MOs.
double

double

Energy

single

Energy

28

Ab initio Methods
Post HF
Configuration Interaction

With this idea, the total wave-function could be written as a linear

combination of determinants (Eq. 37).

(37)

29

Ab initio Methods

(38)

Full CI calculations are possible only for very small

molecules, because the promotion of electrons into virtual
orbitals can generate a huge number of states unless we have
only a few electrons and orbitals.

30

Ab initio Methods

To study big systems or use big basis, the expansion of

configurations are truncated allowing only certain excitations.
The easy way to do it is taking into account only simple and
doble excitations, known as Configuration Interaction of Single
and Doble states (CISD)

(39)

31

Ab initio Methods

The CI Method

1)
2)
3)
4)
5)

Start with a basis set functions.

Make a SCF calculation to obtain the OM SCF occupied
and virtual.
Use those MO to form configuration functions.
Write the wave function as a linear combination of
configuration functions.
Use the variational principle to obtain determinat
coefficients.

32

Ab initio Methods

Perturbation Theory
The basic idea of perturbation theory is to expand the energy
and wave-functions of the perturbed system in power series.

(40)

33

Ab initio Methods

(41)

(42)

34

Ab initio Methods

It is assumed that the correction factor is small compared

to the initial Hamiltonian for this reason the perturbed wave
function and energy can be expressed in the form of Taylor
expansion in powers of the perturbation parameter.

(43)

(44)

35

Ab initio Methods

The perturbed Schrdinger equation (eq. 41) can be

written as:

(45)

In general form this equation can be written as:

(46)

36

Ab initio Methods

With the condition:

after several steps Eq. 46 give us a set of equations:

37

(47)

Ab initio Methods

Multiplying each of these equations (Eq. 47) by:

Using the orthonormality relation:

And the relation:

38

Ab initio Methods

We obtain the following expressions for the nth-order

energies:

(48)

.
.
.
.

39

Ab initio Methods

The Mller-Plesset Perturbation

When the operator H0 is the Fock operator has the name of
Mller-Plesset perturbation theory (MPPT), the more used.
If MPPT is a power series of second order is called MP2 and is
used generally for geometry optimization. When the power
serie is of fourth order is called MP4 and so on.
Perturbative methods are self-consistent in size in contrast with
Configuration Interaction methods then there is no problem
if we truncate the power series.

40

Ab initio Methods

The Coupled Cluster Method

The coupled cluster method was introduced by Coester and
Kmmel in 1958. It is a numerical technique used for describing
many electron systems.

41

Ab initio Methods

The wave-function of the CC theory is written as an exponential:

(49)

42

Ab initio Methods

(50)

43

Ab initio Methods

Depending on how many terms are actually included in the

summation for T, one obtains coupled cluster doubles (CCD),
coupled cluster singles and doubles (CCSD) or coupled cluster
singles, doubles and triples (CCSDT) method and so on.

(51)

(52)

(53)

44

Ab initio Methods

45

Ab initio Methods

Time of processor consumed to calculate the energy of a compound

related to its molecular formula and theory level used for calculations
46

Ab initio Methods

47

Ab initio Methods

Improvement of Correlation Treatment

Hartree-Fock

CISD

MP2

MP4(SDTQ)

Full CI

STO-1G
STO-3G

Improvement of Basis Set

3-21G

6-31G

Infinity
base set

Exact solution of Schrdinger

equation

Hartree-Fock limit

48

Advantages
Useful for a wide range of systems.
Able to calculate transition states and excited states.
Rigorous accuracy.
Predicted properties of novel compounds.

Disadvantages
Require large computer resources.
Applicable efficiently to systems of tens of atoms.

49

Ab initio Methods

CONCLUSIONS
In general, ab initio calculations give very good qualitative
results and can yield increasingly accurate quantitative results
as the molecules become smaller. The advantage of ab initio
methods is that they eventually converge to the exact solution,
in general the relative accuracy of results is
HF<<MP2<CISD MP4 CCSD<CCSD(T)<CCSDT<FULL CI
however, this convergence is not monotonic. Sometimes, the
smallest calculation gives very accurate result for a given
property. There are 4 sources of error in ab initio calculations:

50

1.
2.
3.
4.

The Born-Oppenheimer approximation

The use of an incomplete basis set
Incomplete correlation
Omission of relativistic effects

ab initio methods are expensive, they often take enormous

amounts of computer CPU time, memory, and disk space. HF
method scales N^4, with N referring to basis functions. Correlated
calculations calculations scale more than this, in practice extreme
accurate solutions are only feasible if the molecule contains dozen
electrons or less. However, results with an accuracy rivaling that of
many experimental techniques can be obtained for moderate-size
organic molecules. Minimally correlated methods, such as MP2 and
GVB, are often used when correlation is important to the
description of large molecules.

51

Ab initio Methods

Erwin Rudolf Josef

Alexander Schrdinger
William Rowan Hamilton

Christian Mller

Milton S. Plesset

Sir John Pople

Max Born

J. Robert Oppenheimer

Christian Mller

Wolfgang Ernst Pauli

Joseph-Louis Lagrange

Carl Friedrich Gauss

52