MSc by Research Theoretical Physics / Programme details

Knowledge covering the ‘principles of modern physical chemistry’ is presented primarily in lectures.  This material is reinforced in workshops and laboratory components, in which students are expected to participate and demonstrate their understanding of the topics.

The unit aims to: present core physical chemistry courses on statistical thermodynamics, potential energy surfaces, photochemistry and physical-organic chemistry and related laboratory experiments.

On successful completion of the course students should be able to:

• select and apply the tools of statistical thermodynamics to predict gaseous properties;
• apply the concepts of potential energy surfaces and transition-state theory to explain the basis of chemical reaction dynamics and dynamics for small molecules;
• apply the principles of physical and physical-organic chemistry to measure and rationalise structure, properties and chemical reaction mechanisms. 
 

Statistical Thermodynamics (6 lectures)
• Introduction.  Boltzmann distribution.
• Molecular partition function (translational, rotational, vibrational, electronic)
• Molecular energy.  Internal Energy.  Entropy.
• Ensembles.  Canonical partition function.  Helmholtz energy.  Pressure.
• Gibbs Energy.  Equilibrium constant.
• Example class.

Chemical Properties from Potential Energy Surfaces (7 lectures)
• potential energy surfaces (PES): Born-Oppenheimer approximation; revision of stationary points & reaction coordinate for collinear triatomic reactions; reaction dynamics on a PES; early and late transition states; reactant/product energy partitioning; use in chemical lasers
• thermodynamic properties derived from PES: thermal corrections and internal energy, enthalpy and entropy; adiabatic and diabatic descriptions of the PES; Evans-Polanyi model; Hammond’s postulate; non-adiabatic dynamics
• transition state theory and the Eyring equation: assumptions, derivation, symmetry and statistical factors, criticisms, tunnelling; kinetic isotope effects; detailed application to the F + H2 reaction.

Photochemistry (5 lectures)
• the basic laws of photophysics and photochemistry: absorption, stimulated emission and spontaneous emission; electronic excited states described using PE surfaces; the Born-Oppenheimer and Franck-Condon principles revisited; spin multiplicity, photophysical processes (luminescent and non-radiative); Jablonski diagrams; quantum yields; quenching and the Stern-Volmer approach.
• excited states and their role in chemistry and spectroscopy: fates of an excited state; photodissociation; Norrish reactions; atmospheric photochemistry - stratospheric ozone and tropospheric oxidation via OH radicals; photochemistry in unsaturated organic species, Woodward-Hoffman correlation rules;
• experimental measurement of photochemical processes: light sources for photochemistry and spectroscopy; incandescent sources; lasers and LEDs; synchrotrons; pulsed radiation; principles of high-resolution and ultrafast spectroscopy.

Modern Physical Organic Chemistry: (6 lectures)
•  The relationship between free energy change, equilibrium constant and reactivity
•  The physical concepts necessary for the design of experiments to test or establish a reaction mechanism, and the application of physical methods to mechanistic problems
•  The effects of structural variation and change of reaction conditions on organic reactivity
•  Types of supramolecular interactions and their relative strengths
•  Some applications of supramolecular chemistry
 

Problem-solving skills, numeracy and mathematical skills, analytical skills. Investigative skills and academic writing.

Feedback through workshops and blackboard quizzes and individual and group discussions with graduate teaching assistants/staff in the laboratory component.

P Atkins and J de Paula, Atkins’ Physical Chemistry (10th Ed), OUP, 2014
A. Maczek, Statistical Thermodynamics Oxford Chemistry Primers, 58, OUP, 1998
C.E. Wayne and R.P. Wayne, Photochemistry, Oxford Chemistry Primers, 39, OUP, 1996
J.I. Steinfeld, J.S. Francisco & W.L. Hase, Chemical Kinetics and Dynamics, Chapters 7 & 10.
H. Maskill, The Physical Basis of Organic Chemistry OUP, 1985. ISBN 9780198551997
E V Anslyn and D A Dougherty Modern Physical Organic Chemistry (University Science Books, 2006) ISBN 9781891389319
J W Steed and J L Atwood Supramolecular Chemistry (Wiley, 2000) ISBN 0471987918
P Beer, P Gale and D K Smith, Supramolecular Chemistry, OUP, 1999. ISBN 9780198504474