MOLECULAR

PHYSICS
Part I
Prepared by Catherine Paschal
Mwenge Catholic University

Catherine Paschal @MWECAU 1

Introduction
• Molecular physics is the study of the physical properties
of molecules and of the chemical bonds between atoms
that bind them.
• Its most important experimental techniques are the
various types of spectroscopy.
• The field is closely related to atomic physics and
overlaps greatly with theoretical chemistry, physical
chemistry and chemical physics.
• In a molecule, both the electrons and nuclei experience
similar-scale forces from the Coulomb interaction.
• However, the nuclei remain at nearly fixed locations in
the molecule while the electrons move significantly.
Catherine Paschal @MWECAU 2
Introduction
• This picture of a molecule is based on the idea that
nucleons are much heavier than electrons, so will move
much less in response to the same force.
• When atoms join into molecules, their inner electrons
remain bound to their original nucleus while the outer
valence electrons are distributed around the molecule.
• The charge distribution of these valence electrons
determines the electronic energy level of a molecule, and
can be described by molecular orbital theory, which
closely follows the atomic orbital theory used for single
atoms.

Catherine Paschal @MWECAU 3

Introduction
• Additionally to the electronic excitation states which are
known from atoms, molecules are able to rotate and to
vibrate.
• These rotations and vibrations are quantized, there are
discrete energy levels.
• The smallest energy differences exist between different
rotational states, therefore pure rotational spectra are in
the far infrared region (about 30 - 150 µm wavelength)
of the electromagnetic spectrum.

Catherine Paschal @MWECAU 4

Introduction
• Vibrational spectra are in the near infrared (about 1 - 5
µm) and spectra resulting from electronic transitions are
mostly in the visible and ultraviolet regions.
• From measuring rotational and vibrational spectra
properties of molecules like the distance between the
nuclei can be calculated.
• One important aspect of molecular physics is that the
essential atomic orbital theory in the field of atomic
physics expands to the molecular orbital theory.

Catherine Paschal @MWECAU 5

Introduction
• An exact solution of the Schrödinger equation for a
molecule is not possible because even the simplest one
consists of two nuclei and one electron.
• To simplify the solution, Born-Oppenheimer
approximation is therefore adopted, in which it is
assumed that the nuclei may be treated as stationary while
the electrons move around them.
• This approximation is fairly valid as the nuclei are much
heavier than an electron.

Catherine Paschal @MWECAU 6

Introduction
• Two such approaches are there for the calculation of
molecular structure, the Molecular Orbital (MO) and the
Valence Bond (VB) methods.
• Most of the modern computational works make use of the
MO theory.

Catherine Paschal @MWECAU 7