Symmetry and MOT-I

In chemistry, symmetry is not simply to do with beauty. It affects

the properties of molecules. Symmetry is central to spectroscopy,
chemical bonding model and many other aspects of the molecular
sciences…..
The Molecular Orbital Model
 Experimental Results

• Oxygen is paramagnetic, consistent with having two unpaired

electrons. In addition, photoelectron spectroscopy (PES) can be
used for determining orbital energies in molecules. The molecule
is bombarded with UV or X-rays to remove an electron from the
molecule. The kinetic energy of the emitted electron is
measured and subtracted from the incident radiation to
determine the binding energy of the electron.

The result is a spectrum of absorptions which are correlated to

the molecular orbitals of the molecule. In addition, electrons
ejected from bonding (and antibonding) orbitals show more
vibrational energy levels than electrons emitted from non-
bonding orbitals.
PES of H2

(Note: IE for H atom = 13.6 eV)

The multiple peaks are due to

electrons ejecting from a range
of stimulated vibrational energy
levels
PES of N2
PES of O2
Variation of energy levels for atomic orbitals of some elements
H Li Be B C N O F
_2s_ _
_2p _ _ _ 2p
_ 2s _ _ _ 2p
_ 1s _ _ _ 2p
_ 2s _ _ _ 2p
_ 1s _ _ _ 2p
_ 2s _ _ _ 2p
_ _ _ 2p
_ 1s _ 2s

_ 2s

_ 1s _ 2s

_ 2s

_ 1s

_ 1s

_ 1s

_ 1s
the decrease in orbital energy of the MOs across the period
from Li2 to F2. This is caused by the increasing nuclear charge:
The molecular orbital model is
by far the most productive of
the various models of chemical
bonding and serves as the
basis for most quantitative
calculations, including those
that lead to many of the
computer-generated images. In
its full development, molecular
orbital theory involves a lot of
complicated mathematics, but
the fundamental ideas behind it
are quite easily understood.