Quantum chemistry:

the chemical bond

Introductory concepts
The chemical bond, a link between atoms, is
central to all aspects of chemistry.

Reactions…………………..?

The physical properties of individual molecules and of

bulk samples of matter also stem in large part from the
shifts in electron density that take place when atoms
form bonds.
The theory of the origin of the numbers, strengths,
and three-dimensional arrangements of chemical
bonds between atoms is called valence theory.

There are two major approaches to the calculation

of molecular structure, valence bond theory (VB
theory) and molecular orbital theory (MO theory).

Almost all modern computational work makes use

of MO theory, and we concentrate on it in this
chapter. Valence bond theory, though, has left its
imprint on the language of chemistry, and it is
important to know the significance of terms that
chemists use every day.
The classification of bonds

two types of bond:

a. An ionic bond is formed by the transfer of electrons
from one atom to another and the consequent
attraction between the ions so formed.
b. A covalent bond is formed when two atoms share a
pair of electrons.
Lewis’s original theory was unable to account for
the shapes adopted by molecules. The most elementary
but qualitatively quite successful explanation of
the shapes adopted by molecules is the valence-shell
electron pair repulsion model (VSEPR model).

The Lewis theory of covalent bonding is :

1. Arrange the atoms as they are found in the molecule.

2. Add one electron pair (represented by dots, :)
between each bonded atom.
3. Use the remaining electron pairs to complete the octets
of all the atoms present either by forming lone pairs or
by forming multiple bonds.
4. Replace bonding electron pairs by bond lines (–) but
leave lone pairs as dots (:).
Potential-energy curves

1
Do  De  hv
2

The graph is called a potential energy curve because

the nuclei are stationary and contribute no kinetic
energy.
The Born–Oppenheimer approximation
All theories of molecular structure make the same
simplification at the outset.

All theories of molecular structure adopt the Born–

Oppenheimer approximation.

In this approximation, it is supposed that the nuclei, being

so much heavier than an electron, move relatively slowly
and may be treated as stationary while the electrons move
around them.
The hydrogen molecule ion H2+ is the simplest molecule,

The Schrodinger equation for the hydrogen molecule ion

is
where n(RA, RB ) is the wavefunction for nuclear
motion.

The Schrodinger equation for electronic motion is

then

with the Hamiltonian for electronic motion given by

The Born–Oppenheimer approximation shows that the
nuclei move in the potential energy Ee(R ) determined by
the electronic motion, so the Schrodinger equation for
nuclear motion becomes

where En is the energy of nuclear motion, which contains

contributions for translational motion, rotational motion,
and vibrational motion.
The wavefunction for nuclear motion n(RA, RB) is the
product of wavefunctions for translational, rotational, and
vibrational motions.