1. Explain the Density Functional Theorem.

DFT has become very popular in recent years.

• It is computationally less intense than other methods with similar accuracy.

• The principal of DFT is that the energy of a molecule can be determined from
electron density instead of wave function.
• This theory originated with a theorem by Hohenberg and Kohn and practical
application of thin theory was developed by Kohn and Ham formulated a method
similar to that in a HF method.
• In this formulation the electron density is expressed as a linear combination of basis
function similar to HF orbital .A determinant is formed from these functions called
Kohn-Ham orbitals. It is the electron density from this determinant that is used to
compute the energy. KS orbital describes the behavior of electrons in a molecule
fast as the HF orbital.
The Hohenberg and Kohn theorem
• Every observable of a stationary quantum mechanical system can be calculated
from the ground state density alone i.e. every observable can be written as a
function of the ground state of the electron density .That is given the ground state
electron density function γ0(x,y,z) we can in principal calculate any grounds state
property
Eg: Energy E0.
γ0(x, y, z) → E0
• The electron density function will be given energy higher than the true ground state
energy. In DFT the electric energy from a trial electron density is the energy of the
electrons moving under the potential of the atomic nuclei.
The Kohn-Sham method (KS)
• Method of combining the wave function and electron density approach.
• The two basic ideas are:-
1. To express the molecular energy as a sum of terms, only one of which forms the
unknown functional .Thus even moderately large errors in this term will not induce
large error in the total energy.
To use an initial guess of the electron density γ in the K-S equation s, to calculate an
initial guess of the K-S orbitals and energy levels. The final K-S orbitals are used to
calculate an electron density that in turn is used calculate energy.
Types of calculations in DFT
• The local density approximation(LDA)
It is based on the assumption that at every point in the molecule the electron density
has the value that would be given by a homogenous electron gas which has the same
electron density.
• The generalized gradient approximation (GGA)
Most DFT calculations nowadays use exchange correlation energy functional that
𝜕 𝜕 𝜕
utilize both the electron density and its gradient.(𝜕𝑥 + 𝜕𝑦 + 𝜕𝑧)γ= -Δγ
• Hybrid functional
 Includes an energy contribution from the HF type electron exchange .1st popular
successful hybrid method was B3LYP.

4. What are four useful chemical properties (quantities) that DFT calculates?
i. Phase Transformations: We can predict various phase transformations that takes place
under mechanical strain.
ii. Structural properties: Geometries of various organic molecules can be determined.
Defect structure as vacancy, grain boundary etc can be estimated. Surface structures and
adsorption can be predicted for variety of systems.
iii. Mechanical properties: We can predict various mechanical properties like Elastic
Modulus, Compressibility and Thermal expansion coefficients of given material.
iv. Thermodynamic properties: Formation energy of the materials can be estimated.
v. Phase Diagram: By calculating which is phase is stable at various composition and
various temperatures we can plot phase diagram.
vi. Transport properties: Diffusion rate of vacancy, interstitial etc. can be quantified by
calculating migration barrier to diffusion of these species.
vii. Electronic and electrical properties: Band structure, Dipole moment of molecule,
interface, conductivity of materials, ionization energies and electron affinity can be
calculated using DFT methods
viii. Optical properties: Luminescence and fluorescence of materials can be found using
DFT.
ix. Chemical properties: Rate of reaction and chemisorptions of various gases at various
surfaces can be established.

5. What are slater type orbitals? How they are different from Gaussian type orbitals?

• Slater type orbitals

When we calculate the energy of molecules using perturbation or variation theory
there is 5-6% discrepancy with the experimental total E. One way to improve our
results is to use a more general trial function than used in the above methods.
Because a suitable trial function may be almost any function we are not restricted
to choose a H like wave function. For eg: In 1930 the American physicist John
slater introduced a set of orbitals newly called slater orbitals which are of form
S(n,l,m)(r,Ɵ,φ) = Nnlrn-1e-x Ylm(Ɵ,φ)
Where, Nnl = (2χ)n+12/(2n!)1/2
Ylm(Ɵ,φ) –Spherical harmonics. χ is an arbitrary constant and is not necessarily
equal to z/n as the H like orbitals.Radial parts of the slater orbitals do not have
nodes like H atomic orbitals do. slater- type orbitals represent the real situation for
the electron density in the valence region and beyond, but are not so good nearer to
the nucleus.
• Gaussian type orbitals
Although slater orbitals were used for many years they are not used directly
anymore because the integrals in the resulting secular determined are difficult to
evaluate. If we use Gaussian functions instead of Slater orbitals, however all the
 multicentre integrals (integrals involving more than one nuclear centre) are easy to
calculate.
G(n,l,m)(r,Ɵ,φ) = Nnrn-1𝑒 −𝛼𝑟^2 Ylm(Ɵ,φ)
Both Gaussian and Slater orbitals have very different behavior for small values of
r.

STO

GTO

The Gaussian orbitals does a reasonably good job of describing the Slater orbitals
for values of r>a0 but underestimate the magnitude for values of r<a0.

6. What are molecular mechanics methods in computation chemistry? Discuss.

• Molecular mechanics is based on a model of a molecule as a collection of balls

(atoms) held together by springs (bonds). If we know the normal spring lengths and
angles between them, and how much energy it takes to stretch and bend the springs,
we can calculate the energy of a given collection of balls and springs i.i; of a given
molecule changing the geometry until the lowest energy is found enables us to do
geometry optimization ie, to calculate a geometry for the molecule. Molecular
mechanics is fast a fairly large molecule like a steroid (eg: cholesterol,C27H46O)can
be optimized in seconds on a good personal computer.
• Molecular mechanics (MM) computes the structure and energy of molecules based
on nuclear motions. In this method electrons are considered explicitly, but rather it
is assumed that they will find their optimum distribution once the positions of the
nuclei are known. This assumption is a based on the Boen-Oppenheimer
approximation that nuclei are much heavier than electrons and their movement is
negligibly small compared to the movement of e3lctrons. The molecular mechanics
method (MM) also called empirical force field (EFF) method is different from the
semi empirical methods.
• The potential functions and the parameters used for evaluating interactions are
termed a force field and molecular mechanics methods are sometimes called force
 fields methods. The term arises because the negative of the 1st derivative of the
potential energy of a particle with respect to displacement along some direction is
the force on the particle; a “force field” E(x, y, z coordination of atoms) can be
differentiated to give the force on each atom.

7. What is meant by semiempirical MO treatment?

Semiempirical methods modify Hartree-Fock (HF) calculations by introducing functions

with empirical parameters. These parameters are adjusted with experimental conclusions to
improve the quality of computation. The real cost of computation is due to the two-electron
integrals in the Hamiltonian that has been simplified in this method. Semiempirical methods are
based on three approximation schemes.

1. The elimination of the core electrons from the calculation.

Inner electrons do not contribute towards chemical activity, which makes it possible to
remove the core electron functions from the Hamiltonian calculation. Normally, the entire core
(the nucleus and core electrons) of atoms is replaced by a parameterized function. This has the
effect of drastically reducing the complexity of the calculation without a major impact on the
accuracy.

2. The use of the minimum number of basis sets.

In this approximation, while introducing the functions of valence electrons, only the
minimum required number of basis sets will be used. This technique also reduces the complexity
of computation to a large extent.

3. The reduction of the number of two-electron integrals.

This approximation is introduced on the basis of experimentation rather than chemical

grounds. The majority of the work in ab initio calculations is in the evaluation of the two electron
integrals (Coulomb and exchange). All modern semiempirical methods are based on the modified
neglect of differential overlap (MNDO) approach. In this method, parameters are assigned for
different atomic types and are fitted to reproduce properties such as heats of formation, geometrical
variables, dipole moments, and first ionization energies. The parameterization was carried out
separately for classes of compounds like hydrocarbons, CHO systems, CHN systems, and so on.
The latest versions of the MNDO method are referred to as AM1 and PM3. Another method to
reduce the two-electron integral is the zero differential overlap (ZDO) approximation, which
neglects all products of basis functions depending on the same electron coordinates when located
on different atoms.

8. What are the steps involved in identifying HOMO visualization of molecular orbitals?
HOMO visualization of molecular orbitals can be done by the use of quantum
chemical softwares such as GAMESS.It requires the selection of method and basis set and the
specification of the geometry of the molecule.
 The common methods are:
(1) Hartree – Fock(HF) –(RHF,ROHF,UHF,etc)
(2) Moller – Plesset second order ,third order,etc.(MP2,MP3,MP4,etc)
Basis set:The set of functions used to approximate the orbitals.
Eg: STO – 3G,6- 31 G,etc.
The specification of geometry – The most common methods is Z – matrix, Cartesian
coordinates and unique coordinates.
To find the HOMO, the calculation type should be optimization. If the molecule is
neutral, give the charge as 0. If the electrons are paired, multiplicity is one. Any basis set
can be used.
Eg: Determination of HOMO of water molecule.
Identify the point group.
Obtain the z-matrix.
O
H 1 1.0
H 1 1.0 2 109.0
The input file is saved and run the program. The output file will give the HOMO.The
number of occupied orbitals will be half the number of electrons.HOMO is the highest
among occupied orbitals. For water 5TH molecular orbital is HOMO.The wxMacMolplt
program is used to display the desired orbital. Select the output file and view the molecule.
OR any suitable example.

9. Pick out the importance features of force fields for MM3 and MMFF.

(i) MM3
The MM family of force fields (MM2, MM3, and MM4) was introduced by Allinger et al.
and is widely used for the computations of small molecules. The force field can identify sp, sp2
and sp3 hybridized carbon atoms, organic intermediates such as free radical and carbocation, the
carbonyl functional group, and cyclohydrocarbons such as cyclopropane and cyclopropene. The
MM family was parameterized to fit values obtained through electron diffraction, which provide
mean distances between atoms averaged over vibrational motion at room temperature. In MM2,
expansion is made up to cubic terms, which may cause the cubic function to pass through a
maximum that is far from the reference value. This has lead to disastrous expansion of bonds in
some experiments. This defect is overcome in MM3 by limiting the use of the cubic contribution
only when the structure is sufficiently close to its equilibrium geometry and is inside the actual
potential well.
Leach includes a quartic term in MM3, which eliminates the inversion problem and leads
to an even better description. MM2 has a similar defect with bond bending and is corrected in
MM3. Most of the force fields agree to a point-charge electrostatic model, where the point of
origination of a charge is assigned to a particular atom. Hence, the MM family assigns dipoles to
the bonds in the molecule. The electrostatic energy is then given by a sum of dipole-dipole
interaction energies. This approach can be irresistible for molecules (ions) that have a formal
charge and which require charge-charge and charge-dipole terms to be included in the energy
expression.
(ii) MMFF
The Merck molecular force field (MMFF) (Halgren, 1996) is similar to MM3 but differs
in focus on its application to condensed-phase processes in molecular dynamics. It achieves MM3-
like accuracy for small molecules and is applicable to proteins and other systems of biological
significance. It is designed to be a transferable force field for pharmaceutical compounds that
accurately treats conformational energetic and nonbonded interactions. This force field is adequate
for both gas phase and condensed phase calculations. It has a large number of cross terms, which
is the major reason for its transferability. The internal bonded terms used in this force field are
bonds, angles, stretch-bend, out-of-plane bending, and dihedrals. Nonbonded terms include van
der Waals and electrostatic.

11. What are the basic principles of configuration interaction?

Configuration interaction (CI) wave function is a multiple determined wave function. This is
constructed by starting with HF wave function and making new determinants by promoting
electrons from the occupied to unoccupied orbitals.The HF terms and the additional terms each
represent a particular electronic configuration, and the actual wave function and the electronic
structure of the system can be conceptualized as the result of the interaction of these
configurations.This electron promotion,which make it easier for electron to avoid one another,is a
physical idea behind the Moller – Plesset(MP) method;the MP and CI methods differ in their
mathematical approaches. Configuration Interaction calculations are be very accurate, but the cost
in CPU time is very high.
CI calculations are classified by the number of excitations used to make each determinant.If
only one elaectron has been moved for each determinant, it is called a configuration interaction
single excitation(CIS) calculation.CIS calculation give an approximation to the excited state of the
molecule,but donot change the ground state energy.Single and double excitation(CISD)
calculations yield aground state energy that has been corrected for correlation.Triple excitation
(CISDT) and quadruple excitation (CISDTQ) calculations are done only when very high accuracy
results are desired.
The CI calculations with all possible excitations is called a full configuration
Interaction(FCI).FCI calculation using an infinitely large basis set will give an exact quantum
mechanical result.However, full CI calculations are very rarely done due to immense amount of
computer power required.

12. Discuss the Hartee-Fock method.

The most common type of ab initio calculation. Primary approximation is the central field
approximation. This means that the coulombic electron- electron repulsion is taken into account
by integrating the repulsion term. This gives the average effect of the repulsion but not the explicit
repulsion interactions. This is a variational calculation meaning that the approximate enegy
calculated are equal to or greater than the exact energy. The energies are calculated in units called
Hartree. Because of the central field approximation the energies from these calculations are always
greater than the exact energy and tend to a limiting value called the Hartree Fock limit as the basis
set is improved.
Advantage- It breaks the many electron Schrodinger eqn into many simpler one electron
eqns.Each one electron eqn is solved to yield a single electron wave function called an orbital and
an energy called an orbital energy. The orbital describes the behavior of an electron in the net field
of all the other electrons.
The second approximation in the Hartree Fock calculation is due to the fact that the wave function
must be described by some mathematical function which is known exactly for only a few one
electron systems. The functions used most often are Gaussian type orbitals (GTO) e-ar2 . the wave
function is formed from linear combination of atomic orbitals or basic functions. Because of this
approximation most Hartree Fock calculations give a computed energy greater than the Hartree
Fock limit.
The exact set of basis functions used of x

13. What are the basic principles of Moller Plesset Perturbation Theory?

The basic idea behind the perturbation theory is that if we know how to treat a simple system then
a more complex version of the system, if it is not too different, can be treated mathematically as
an altered or perturbed version of the simple one. There is a hierarchy of Moller – Plesset energy
levels – MP0,MP1,MP2 etc. which successively account more thoroughly for the electronic
repulsion.
MP0 – use electronic energy obtained by simply summing the Hartree – Fock one electron energy.
Ignores inter electronic repulsion- refuse to allow more than two electrons in the same spacial MO.
MP1 – MP0 correlated with the coulomb and exchange integral. ie. MP1 is just the Hartree – Fock
energy.
MP2 – Hartree Fock energy + a correction term that represents a lowering of energy brought about
by allowing the electrons to avoid one another better than in the Hartree Fock treatment.

14. What is meant by Koopman’s theorem? What are its applications?

Koopmans' theorem states that in closed-shell Hartree–Fock theory, the first ionization energy of
a molecular system is equal to the negative of the orbital energy of the highest occupied molecular
orbital (HOMO).
Koopmans' theorem is exact in the context of restricted Hartree–Fock theory if it is assumed that
the orbitals of the ion are identical to those of the neutral molecule (the frozen
orbital approximation). Ionization energies calculated this way are in qualitative agreement with
experiment – the first ionization energy of small molecules is often calculated with an error of less
than two electron volts. Therefore, the validity of Koopmans' theorem is intimately tied to the
accuracy of the underlying Hartree–Fock wavefunction.