LECTURE NOTE-1

Module1

Quantum Mechanics for Computing Properties of Molecular System

Our aim is to create an appropriate model of a molecular system of our interest, and to
compute microscopic and macroscopic properties of the system. Quantum mechanics is
a suitable tool for obtaining molecular properties (mostly at the microscopic level). For
e.g. to predict the structure of H2 molecule in gasphase, i.e. the equilibrium internuclear distance of H2 , one can carry out quantum mechanical calculations to determine
potential energies of the H2 molecule at various internuclear distances. The distance

Potential Energy

with the lowest potential energy will be the most stable structure of H2 ; see Figure 1

Internuclear distance

Figure 1: Sketch of a potential energy curve for diatomic molecules

CHM695, Molecular Modeling, (c) N. N. Nair; Page No: 1

In order to obtain energy using quantum mechanics, one needs to solve the Schroedinger
equation (SE)
= E
H

(1)

where the Hamiltonian operator H is given by the sum of the kinetic energy operator
and potential energy operator (U). Hamiltonian operator can be written knowing
(T)
the atomic/molecular system that we would like to study. The unknown quantities are
and E, where is the total wavefunction of the system, and E is the total energy.
SE in the above form is a differential equation (for 1-dimensional systems) or a partial
differential equation (for dimensions greater than 1), and has to be solved to obtain
and for allowed values of E. The latter is determined by the boundary conditions. is
the wavefunction and has a rich of information regarding the system.

The Hamiltonian operator can be expressed (in atomic units) for a system of N nuclei
and n electrons (see Figure 2) as,
N
n
N n
n
N Z Z
1
1 2
ZI
1
I J
2

H =
+ +
I i
.
2M I
2
r Ii j>i rij J > I R I J
I
I i
i

(2)

The first two terms represent the kinetic energy of the nuclei and the electrons, respectively. The remaining three terms define the potential part of the Hamiltonian and
represent the attractive electrostatic interaction between the nuclei and the electrons
and the repulsive potential due to the electronelectron and nucleusnucleus interactions, respectively. Here M I is the mass and Z I is the atomic number of a nucleus I.
rij is the distance between electrons i and j, r Ii is the distance between nucleus I and
electron i, and R I J is the distance between the nuclei I and J (see Figure 2).

Thus the SE is a partial differntial equation in high dimensions. Solving these partial
differential equations is not practical for systems with more than two particles. Several
assumptions have to be used in solving for realsitic problems, and we will see these
assumptions in the first part of this module.

CHM695, Molecular Modeling, (c) N. N. Nair; Page No: 2

rij
i
rIi
I

rIj
rJj

rJi
R IJ

Figure 2: Pairwise interparticle interactions when two nuclei (I,J) and two electrons
(i,j) are present.

1.1

BornOppenheimer Approximation

Since nuclei are much heavier than electrons, and thus move slower than electrons, we
can consider that electrons are moving in the field of fixed nuclei. This is called the
BornOppenheimer (BO) approximation. But how can this approximation makes the
calculation simpler?

As we are separating the nuclear motion and the electronic motion, we can consider
that
({ri }, {R I }) = el ({ri }, {R I }) nuc ({R I })

(3)

When we can solve the electronic problem with fixed nuclear positions, the first term
in Eqn. 2, i.e. the kinetic energy of the nuclei, can now be dropped under this approximation while solving for electrons. More importantly, the last term describing the
nuclearnuclear repulsion becomes a parameter since it depends only on the internuclear separation. The rest of the terms in Eqn. 2 can be assembled to define the electronic
Hamiltonian H el ,

N n
n
n
ZI
1
1
+
.
H el = 2i
2
r Ii j>i rij
I i
i

(4)

The electronic Schrdinger equation with H el is

H el el = Eel el .
CHM695, Molecular Modeling, (c) N. N. Nair; Page No: 3

(5)

The solutions of this equation are the electronic wavefunction el and the electronic
energy Eel . Let us define Etot as the sum of the electronic energy Eel and the constant
nuclear repulsion term,
N

Etot = Eel +

J>I

ZI ZJ
.
RI J

(6)

It is very important to note that the wavefunction el el ({ri }; {R I }), is a function

of not only the electronic coordinates, but also of the nuclear coordinates. el will be
different for a different set of nuclear coordinates, since the field due to nuclear charges
changes with nuclear positions.

Now, within the framework of the BornOppenheimer approximation, it is reasonable to assume the nuclear motion happens in the average field generated by electrons.
When nuclei move, electrons immediately come to the equilibrium distribution for the
respective electrostatic field created by the nuclear subsystem. Thus, the total electronic
energy Eel Eel ({R I }) is only a function of the nuclear coordinates. Using Eqn. 3,


*
+
 N 1
N Z Z 


I
J
nuc el 
2 + H el +
= E
(7)
 nuc el
 I 2M I I
RI J 
J>I
(8)
Considering that 2I el = 0,

*
 N 1
N



nuc 
2I + el | H el |el +
 I 2M I
J>I

*
 N 1
N

nuc 
2I + Eel +
 I 2M I
J>I

This shows that the Eel + N

J>I

ZI ZJ
RI J


+
Z I Z J 
= E
 nuc
RI J 

+
Z I Z J 
= E
 nuc
RI J 

(9)
(10)

Etot ({R I }) is the potential energy for the nu-

clear motion. One may obtain the potential energy as a function of nuclear coordinates,
called as potential energy (hyper)surface, as for e.g. in Figure 1, by solving the electronic problem for various nuclear coordinates.

CHM695, Molecular Modeling, (c) N. N. Nair; Page No: 4