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Ab Initio

The document discusses ab initio methods in computational chemistry, emphasizing that these calculations are based on theoretical principles without experimental data. It focuses on Hartree-Fock calculations, detailing the self-consistent field concept, the importance of antisymmetry in wavefunctions, and the approximations involved in these methods. Additionally, it compares Slater Type Orbitals and Gaussian Type Orbitals, highlighting their respective advantages and disadvantages in computational accuracy and efficiency.

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46 views18 pages

Ab Initio

The document discusses ab initio methods in computational chemistry, emphasizing that these calculations are based on theoretical principles without experimental data. It focuses on Hartree-Fock calculations, detailing the self-consistent field concept, the importance of antisymmetry in wavefunctions, and the approximations involved in these methods. Additionally, it compares Slater Type Orbitals and Gaussian Type Orbitals, highlighting their respective advantages and disadvantages in computational accuracy and efficiency.

Uploaded by

karthims02
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Computational Chemistry

Semester II M.Sc Chemistry


M.G University, Kottayam

AB INITIO METHODS

Aby Jimson
Dept Of Chemistry
St. Stephen’s College
Uzhavoor, Kottayam
Ab initio methods in computational
chemistry
 "Ab Initio” means “from the beginning

 This name is given to computations which are derived directly from theoretical principles,
with no inclusion of experimental data

 Most of the time this is referring to an approximate quantum mechanical calculation.


 The approximations made are usually mathematical approximations, such as using a
simpler functional form for a function or getting an approximate solution to a differential
equation.
 The most common type of ab initio calculation is the ‘Hartree Fock’ calculation in which
the primary approximation is called the central field approximation
A review of Hartree Fock Calculations
THE WAY TO HF CALCULATIONS

Hartree and
Hydrogen Variation &
SWE 1 D box 3 D box Hartree Fock
Atom Perturbation
Methods
Self Consistent Field Concept

 An important unsolved problem in quantum mechanics is how to


deal with indistinguishable, interacting particles like electrons
 If particles interact, that interaction must be in the Hamiltonian.
 So until we know where the particles are, we can’t write down the
Hamiltonian, but until we know the Hamiltonian, we can’t tell where
the particles are.
 SCF is an iterative method used to calculate the molecular orbitals
with maximum possible accuracy
Hartree’s Method

 According to Hartree's self-consistent-field (SCF) model of the atom, the motion of each electron in the effective field of
the N-1 others is governed by a one-particle Schrödinger equation.
 It follows that the electrons are independent, and interact only via the mean-field Coulomb potential
 the electrons feel the averaged field of all the other electrons in the system.
 We assume the wavefunction can be written as a Hartree product:
Ψ(𝑟1 + 𝑟2 ) = Ψ1 𝑟1 Ψ2 𝑟2
 The individual one-electron wavefunctions, Ψ1 &Ψ2 are called molecular orbitals.
 This form of the wavefunction does not allow for instantaneous interactions of the electrons.
 Instead, the electrons feel the averaged field of all the other electrons in the system.
 The Hartree form of the wavefunction is sometimes called the independent electron approximation.
Pauli's Exclusion Principle

 Total wavefunction must be antisymmetric with respect to the


interchange of electron coordinates
 The Pauli Principle is a consequence of antisymmetry
 The Hartree wavefunction is not antisymmetric
 Fock modified the Hatrees Equation by adding the concept of
antisymmetry and formulated the Hartree- Fock Equation
Hartree Fock Equation

 The antisymmetrized wavefunction is called the Hartree-Fock


wavefunction.
 It can be written as a Slater determinant
 This ensures the electrons are indistinguishable and are therefore
associated with every orbital
 The HF wavefunction is an antisymmetric wavefunction written in
terms of the one-electron Molecular Orbitals.
 The Schrodinger wave equation 𝐻Ψ
෡ = 𝐸Ψ
 The Hamiltonian is made up of energy terms
෡ =𝑻
𝑯 ෡𝒏 + 𝑻
෡𝒆 + 𝑽
෡ 𝒏𝒏 + 𝑽
෡ 𝒏𝒆 + 𝑽
෡ 𝒆𝒆
 HF theory is the simplest wavefunction-based method
 It relies on the following approximations:
The Born-Oppenheimer approximation
The independent electron approximation
The Linear Combination of Atomic Orbitals Approximation (LCAO)
Central Field Approximation

 The Coulombic electron-electron repulsion is not specifically taken


into account. It's net effect is included in the calculation
 This is a variational calculation, meaning that the approximate
energies calculated are all equal to or greater than the exact energy

 The energies from HF calculations are always greater than the exact
energy and tend to a limiting value called the Hartree Fock limit.
 The second approximation in HF calculations is that the wave
function must be described by some functional form, which is only
known exactly for a few one electron systems.
 Because of this approximation, most HF calculations give a
computed energy greater than the Hartree Fock limit
 A number of types of calculations begin with a HF calculation then
correct for the explicit electron-electron repulsion, referred to as
correlation.
Eg -Moller-Plesset perturbation theory, Configuration Interaction
(CI) etc
 The first step in computational chemistry is the calculation of the
molecular orbitals (MOs) for a given molecule.
 If we can calculate the MOs for a molecule, then we can know lots
of things about the molecule, including
 energy
 electron density
 electrostatic potential
 transition state
 frequency
 A molecular-orbital theory calculation is a mathematical expression
of an electron in a molecule.
 Although there are many types of molecular-orbital functions, here
we will only look at the Slater Type Orbitals (STOs) and the Gaussian
Type Orbitals (GTOs).
STO & GTO

 STOs require more calculating, which takes tremendous amounts of


time, however their calculations have been found to be more
accurate than GTOs. On the other hand, GTOs, although less
accurate, are much faster to calculate than STOs.
 By adding several GTOs, we can mimic the STOs accuracy. As the
number of GTOs used increased, the better they were able to
model the STO equation.
 When using GTOs to model STOs, the new equations are given a
new name. They are identified as STO-nG equations where n is a
constant that represents the number of GTOs used. For instance, two
common equations are the STO-3G and the STO-6G in which 3 and
6 GTOs are used respectively.
HF calculations overview
Advantages Disadvantages

The Born-Oppenheimer approximation Electronic Correlation

The independent electron approximation Consequence: Calculated energy is always


higher than true energy

Central Field Theory The calculated value can only reach a


minimum energy up to Hartree Fock Limit,
which is in turn higher than the true energy

The Linear Combination of Atomic Orbitals The integrodifferential equations are thereby
approximation (LCAO) transformed into
algebraic equations (Roothaan's equations) for
the expansion coefficients
Roothaan equations

 The Roothaan equations are strictly the equations for a closed-shell


Restricted Hartree-Fock
 Numerically much easier than integro-differential equations

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