CHEM2304A: Quantum Mechanics and Spectroscopy

Course Organizer: Prof Helen Fielding

Lecturers: Prof Helen Fielding, Prof Sally Price

Normal prerequisite: This is a course taken by affiliate students with an appropriate

background in physical chemistry.

Units: 0.5

Aims

The aims of this course are to introduce and explain electronic, rotational and electronic
spectra for diatomic molecules and to develop further quantum mechanics.

Objectives

Students will be able to

analyse chemical systems using rotational, vibrational and electronic spectroscopy

apply the fundamental postulates of quantum mechanics to problems with exact and
approximate solutions
use molecular orbital theory with diatomic molecules and Hckel theory with
electron systems

Course Structure

Lectures: 16
Tutorials: 9
Labs: 0

Assessment

Exam: 80% (2 hours). The exam is held in December.

Lab: 0%
Coursework: 20%

Recommended Texts

R Silbey, R A Alberty and M G Bawendi Physical Chemistry 4th Edition John Wiley.
Earlier editions of Ailbey and Alberty are equally useful.

Acceptable alternatives are:

P W Atkins and J de Paula Atkins' Physical Chemistry 8th edition, Oxford 2006; or
earlier editions
R. Chang and J. W. Thoman Jr., Physical Chemistry for the Chemical Sciences,
University Science books.
Further Reading

I N Levine, "Quantum Chemistry", 4th ed, Prentice Hall, 1991

J M Hollas, Modern Spectroscopy", 2nd ed, Wiley, 1992

Course Outline

Spectroscopy of diatomic molecules HHF, 8 lectures

Basics: electromagnetic spectrum, absorption and emission of radiation, transition

moment and selection rules. Rotational spectroscopy: rigid rotor energy levels,
reduced mass, rotation spectroscopy selection rules, intensities of transitions in
rotational spectroscopy
Vibrational spectroscopy: harmonic oscillator, Morse potential, anharmonic oscillator
energy levels, selection rules, dissociation energies, Birge-Sponer extrapolation
Rovibrational spectroscopy: combination differences
Rovibrational spectroscopy workshop
Electronic spectroscopy: principles, term symbols of diatomic molecules, selection
rules
Vibrational structure of electronic transitions, progressions and sequences, vibronic
transition wavenumbers, Deslandres tables, intensities of vibrational components of
electronic transitions (Franck-Condon principle)
Vibronic spectroscopy: dissociation energies, rotational fine structure
Electronic spectroscopy workshop

Quantum Mechanics SLP, 8 lectures

Fundamental principles and postulates: probability interpretation of , operators and

Hamiltonians, eigenvalue equations, Schrdinger equation, expectation values,
Variation principle, more dimensions and particles.
Exact solutions to the Schrdinger equation: harmonic oscillator, particle on a ring,
particle on a sphere (rigid rotor), hydrogen atom.
Beyond exact solutions: helium atom.
Molecular orbitals: Born-Oppenheimer approximation, linear combination of atomic
orbitals, secular equations, two-orbital systems.
Hckel theory for -electron systems.