Department of Chemistry

Glasgow University

COURSE DOCUMENTATION

1999-2000

Chemical Physics-4H/4M

Chemistry Component

Course Head: Dr John H Dymond

Timetable 3

General information 4

Project timetable 6

Safety 6

Guidelines for writing a thesis 7

Booklist 9

Aims & objectives of courses 10

POLICY ON SUMMATIVE ASSESSMENT

All feedback on coursework used in assessment, including mid-year class exam/class test marks and laboratory grades, is strictly provisional for your guidance only, and is subject to ratification by the Board of Examiners and external examiners at the end of the academic year. You must retain all copies of assessed work (lab notebooks, exam scripts, etc.) and have them available for inspection by the examiners if requested at the end of the year. You will be given reasonable advance warning should this be required.

PLAGIARISM

Degrees from Glasgow University recognise personal achievement. Plagiarism or copying is academic fraud and a serious offence against University discipline.

Plagiarism is the submission of someone else’s work as one’s own without acknowledgment. If you use someone else’s work - words, ideas, data - you should say so. Direct quotations should be placed in quotation marks.

This regulation applies to all work submitted for assessment, including lab reports, class tests and research projects unless you have specifically been told otherwise, for example in the case of a group project or when a number of students share experimental data.

1999-2000 CHEMICAL PHYSICS-4H/4M LECTURES: Physical Lecture Theatre

(except as noted below)

Week

Begins

Mon

JD*

RDP

KT*

DMC

Hol

Tues

JD*

RDP

KT*

DMC

Wed

Thur

JD*

RDP

KT*

DMC

Fri

JD*

RDP

KT*

DMC

Thursday, 7th October 10.00 a.m. Class enrolment and talks on

Safety (Dr. Cross) & IT (Dr Tyler) Research Project 4M : 14 weeks

Monday, 25th. October, 1.00 p.m., Organic Lecture Theatre 4H : 12 weeks

Careers for chemists. Speakers from industry, the department and § Thesis Talks:Tues., Wed. & Thurs., Week 18, 2 - 5 p.m.

careers service.

Irvine Review Lectures, St. Andrews, April, 2000.

Room

KT	Dr Tyler	Molecular Spectroscopy	BW	Dr Webster	Modern Molecular Calculations
MK	Dr Kadodwala	Surface Science	KT*	Dr Tyler	Laser Spectroscopy
DL	Dr Lennon	Heterogeneous Catalysis	RDP	Dr Peacock	Chirality
			DMC	Dr McComb	Solid State Chemistry

LH	Dr Hecht [A5-07]	Advanced Group Theory 4M only	JD*	Dr. Dymond	Statistical Thermodynamics 4M only
JD	Dr. Dymond [A5-07]	Intermolecular Forces 4M only

Wed	4 pm Physical Tutorials	Weeks 2-10 Organic or Physical LT
Wed	4 pm Inorganic Tutorials	Weeks 11-17 Organic or Physical LT

ORGANIZATION:

The Chemical Physics Course is organized jointly by the Departments of Chemistry and Physics and Astronomy. The Class Heads are :

Dr John H. Dymond Tel: 0141-330-5949 (direct), Room A5-21 Joseph Black Building,

E-mail: johnd@chem.gla.ac.uk

Dr. A. Watt Tel: 0141-330-4926 (direct), Room 535 (Kelvin Building)

E-mail: s.watt@physics.gla.ac.uk

Please contact them at any time if there are matters that you wish to discuss concerning the course.

ILLNESS AND ABSENCE FROM CLASSES

If you are unable to attend classes you should contact Dr Dymond or Dr. Watt as soon as possible to explain the reasons for your absence. If appropriate, a relevant medical certificate should be submitted.

If you believe that your performance in the course has been adversely affected for reasons which you wish to draw to the attention of the Board of Examiners it is essential that you write to the Class Heads to inform them of the circumstances.

LECTURE COURSES

All courses consist of eight lectures. They will be given in the Physical Lecture Theatre, or in A5-07 (Dr. Hecht’s lectures and Dr. Dymond’s course on Intermolecular Forces), unless otherwise notified.

Molecular Spectroscopy	Dr. Tyler
Surface Science	Dr. Kadodwala
Heterogeneous Catalysis	Dr. Lennon
Advanced Group Theory	Dr. Hecht	4M only
Laser Spectroscopy	Dr. Tyler
Modern Molecular Calculations	Dr. Webster
Chirality	Dr. Peacock
Solid State Chemistry	Dr. McComb
Statistical Thermodynamics	Dr. Dymond	4M only
Intermolecular Forces	Dr. Dymond	4M only

TUTORIALS

Physical: Term 1: Weeks 2-10 Wednesdays at 4 pm in the Organic or Physical Lecture Theatre.

Inorganic: Term 2: Weeks 11-17 Wednesdays at 4 pm in the Organic or Physical Lecture Theatre.

STUDENT PROGRESS

Your performance of class work will be considered satisfactory only if you:

(a) regularly attend lectures and tutorials,

(b) carry out a research project in Chemistry or Physics for 20 hours per week for 14 weeks (4M) or for 12 weeks (4H) following the timetable given later in this handbook,

and, in the case of a Chemistry project:

(d) provide the Chemistry Department with one copy of a thesis on your project by the first day of the third term.

EXAMINATIONS

The Chemistry component of the Chemical Physics final degree examinations consist of a research project and three written papers. There is also a third year carry-over mark.

The research project will be assessed on the basis of the thesis, the work performed during the project, and an oral examination on the contents of the thesis.

As a guide: the project contributes about 15% to the final mark, with the examination papers 36.5%, and the laboratory work 6% in each subject.

All students must be available for oral examination by the external examiners on Tuesday, 15th June, 2000. This is an integral part of the degree examination.

Towards the end of the second term further information will be given about the format of the degree examinations.

CHEMISTRY DEPARTMENT LIBRARY

The Librarian, Mrs Denise Curry, has a selection of recommended textbooks which are available for short term loan. She also keeps a limited supply of tutorial sheets and course handouts.

CAREERS TALK AND DISCUSSION

Monday 25th October 1 pm Organic Lecture Theatre.

"Careers for Chemists" Speakers from industry, the Department and the Careers Service will present their views of possible careers. This will be followed by an open-ended discussion.

Professor Winfield and Dr Muir will arrange individual interviews for all students early in Term 1 to discuss their choices of a future career.

LECTURES

Alchemist Club and local R.S.C. meetings: Attendance at these talks, which are held on Thursdays at 4 pm, and at the Irvine Review Lectures is recommended and encouraged. The Irvine Review Lectures will be given in St. Andrews during April, 2000.

FOURTH YEAR PROJECT TIMETABLE

Project : 14 weeks (4M)

Dr Peacock (RDP) is in overall charge of fourth year projects.

Week 1 Project supervisors announced to class.

Students contact supervisors and agree on projects.

Supervisors give students two copies of a synopsis of the project including a title and leading references.

One copy of the project synopsis should be given to RDP.

Week 2 Practical work begins from the start of week 2. A COSHH form must be completed, signed by the supervisor and given to Mrs M Nutley (Room B4-20a). If the nature of the research changes during the project new COSHH forms must be completed.

Week 4 Project assessors announced.

Students contact assessors.

Week 10 Students give their thesis introduction to the supervisor. The supervisor will return the introduction in the first week of term 2.

The Introduction should be around 5 -10 pages, word processed, and include a full list of references.

Week 17 Friday: Last day of practical work.

Week 18 Thesis talks (15 mins - not assessed).

Week 20 Friday: Final draft of thesis approved by supervisor.

Week 21 Monday: Last day for submission of theses. One copy to be supplied to Mr R Munro - he will make a copy (or copies) for the Department, and bind and return the original.

Weeks 22-23 Oral examinations. These will be conducted by the assessor and a second member of staff. The supervisor will not be present.

SAFETY

The Departmental Safely Committee has issued the following guidelines.

1. Experimental work should normally not start before 9.00 am and should finish by 5.00 pm.

2. Should it be necessary to work outwith these hours for short periods this must be approved by the supervisor and the usual rules of late working will apply. If the supervisor has to leave before experimental work is complete written permission must be given and in such cases a designated proxy ( academic, post-doctoral or senior technical staff) must be present in the building.

3. Access to IT equipment will be available only when Janitors are present in the building.

GUIDELINES FOR PRESENTING AND WRITING A THESIS

The thesis counts for 40% of the marks assigned to the project and, in addition, is the only tangible result of the sixteen weeks of work which can be shown to the External Examiners. It is therefore important that you do not let yourself down by a badly written or produced thesis.

TECHNICAL POINTS

The thesis should be word processed (the Department now has an adequate number of PC’s with WORD 6 installed).

The font should be clear. Fonts normally used are Times New Roman or Arial (usually 10, 11 or 12 point). This document is written in Arial 10pt. with main headings in 12 pt bold.

The thesis should use 1.5 line spacing and have a reasonable margin on the left hand side to allow for binding. (WORD 6 gives default margins of 3.17 cm left and right and 2.54 cm top and bottom which are acceptable).

Pages should be numbered consecutively, as should diagrams and spectra. Since the word processor will do the numbering for you, it is easier if you do not include whole page diagrams or spectra in the page numbering, but this is a matter of choice.

Chemical structures can be drawn using ChemWindow and copied into WORD 6. On the other hand there is nothing wrong with Xeroxing in structures (and indeed diagrams) provided that the result looks neat and clear.
REFERENCES

Referencing work is very important and is frequently badly done. The format shown in the following examples is that employed by the Royal Society of Chemistry. It should be used unless your supervisor suggests an alternative.

1. Journal articles: (Journal in italics, year, volume no in bold, page no)

I. A. Fallis, L. J. Farrugia, N. M. Macdonald and R. D. Peacock, J. Chem. Soc. Dalton Trans., 1989, 931.

P. R. Mallinson and K.W. Muir, J. Appl. Crystallogr., 1985, 18, 51.

other possibilities are:

unpublished work, in press, personal communication.

2. Books: (Title in italics, publisher, place, year, vol no, page if necessary)

International Tables for X-ray Crystallography, Kynoch Press, Birmingham, 1974, vol 4.

3. Theses:

N. M. Macdonald, Ph. D. thesis, University of Glasgow, 1994.

P.A. Lovatt, B. Sc. thesis, University of Glasgow, 1993.

CONTENT

The thesis should contain
Title page

Acknowledgements

Contents page (with page numbers)

A one page Abstract
Introduction

Experimental Section,

Results and Discussion (or Results and Discussion as separate sections)
Conclusions

References

The above is the logical order, but in some areas it is normal to put the experimental section at the end - consult your supervisor.

The INTRODUCTION should set the work in context, review previous work (fully referenced), describe any techniques or theories with which you were unfamiliar when you began the research, and describe what you intended to do.

The EXPERIMENTAL SECTION should give full experimental details of all reactions or experiments carried out. It is particularly important to indicate which are literature preparations and which are novel. If a literature preparation is reported it is important to note if you modified it or if it behaved in an unexpected way. New compounds should be as fully characterised as possible and it is a good idea to include the actual spectra of new compounds.

The DISCUSSION is extremely important and is often where students do not do themselves justice. A project where absolutely nothing has worked can be made interesting by discussing WHY things went wrong. In any case the discussion is often where you show how much of the project you understood!

The CONCLUSIONS should summarise the work and suggest how it could be continued in the future.

The ABSTRACT will be similar to the Conclusions but should be concise and incisive - it is the first thing an examiner will read, and should encourage him or her to read the rest of the thesis!

Finally: SPELL CHECK YOUR THESIS.

CHEMICAL PHYSICS 4H/4M

RECOMMENDED TEXTBOOKS

Physical Chemistry, Second Edition, by R. A. Alberty and R. J. Silbey (John Wiley and Sons, Chichester), 1992, £ 24.95.

Inorganic Chemistry, Second Edition, by D. F. Shriver, P. W. Atkins and C. H. Langford (Oxford University Press), 1994, £ 21.99.

The Mechanisms of Reactions at Transition Metal Sites, by R. A . Henderson (Oxford Science Publications), £ 5.99.

Chemical Bonding Theory, by B. C. Webster (Blackwell Scientific, Oxford), 1990, £ 24.95.

Basic Solid State Chemistry, by A. R. West ((John Wiley and Sons, Chichester), 1990, £ 22.95.

.

Structural Methods in Inorganic Chemistry, Second Edition, E.A.V. Ebsworth, D.W.H. Rankin and S. Craddock, Blackwell, £ 19.95.

This is particularly useful for laboratory and tutorial work and helpful in problem solving.

NOTE : ALL PRICES ARE SUBJECT TO CHANGE BY PUBLISHERS AT ANY TIME

Other books may be recommended by lecturers.

BOOKS AVAILABLE IN THE CHEMISTRY BRANCH LIBRARY

Group Theory in Chemistry and Spectroscopy, by T. S. Tsukerblat (Academic Press), 1994.

Chemical Applications of Group Theory, Third Edition, by F. A. Cotton (John Wiley and Sons, Chichester), 1990.

Fundamentals of Molecular Spectroscopy, Fourth Edition, by C. N. Banwell (McGraw-Hill, London), 1994.

Heterogeneous Catalysis. Principles and Applications, G. C. Bond (Oxford University Press).

Crystal Structure Analysis: a Primer, Second Edition, J. P. Glusker and K. N. Trueblood (Oxford University Press).

Tables for Group Theory, P.W. Atkins, M.S. Child and C.S.G. Phillips (Oxford University Press).

Molecular Quantum Mechanics, Second Edition, P.W. Atkins (Oxford University Press).

Modern Spectroscopy, Third Edition, J.M. Hollas (John Wiley).

Symmetry and Structure, S.F.A. Kettle (John Wiley).

Physical Chemistry, Sixth Edition, P.W. Atkins (Oxford University Press).

Title: Molecular Spectroscopy

Lecturer: Dr J K Tyler

Aims: This course aims to cover the fundamentals of molecular spectroscopy and to show how details of molecular structure can be deduced from the study of rotational, vibrational and electronic spectra of molecules.

Objectives:

After this course the student should understand the basic principles underlying the following topics:

1. Energy changes and spectroscopic transitions. Units of spectroscopic measurements.

2. The Born-Oppenheimer approximation. The Boltzmann distribution and the population of molecular energy states.

3. The basis of selection rules. Spontaneous and stimulated transitions. Spectral line shapes. The principles of laser action.

4. Rotational spectra of molecules in the microwave and far-infrared regions.

5. Vibrational spectra of molecules in the infrared region.

6. Rotational and vibrational Raman spectroscopy.

7. The elucidation of detailed molecular structures from spectroscopic measurements.

Outline:

Molecular energy changes and molecular spectra. Spectroscopic units. The Born Oppenheimer approximation and molecular motions. The Electromagnetic Spectrum. The interaction of e.m. radiation and matter. Einstein A and B coefficients. The Boltzmann distribution. Spectroscopic selection rules. Principles of laser action.

Rotational angular momenta and energy levels. Classification of molecular rotors through principal moments of inertia. Details of selection rules and resulting spectra. Effects of applied electric fields - the Stark effect. The determination of electric dipole moments. Molecular structure elucidation. Practical considerations.

Vibrational spectra in the infrared region. The harmonic and anharmonic models for the diatomic molecule. The Morse potential. Polyatomic molecules and normal modes of vibration. Group frequencies. Rotational fine structures in molecular vibration spectra. Experimental aspects.

Light scattering and Raman specroscopy. Rayleigh and Raman scattering. Virtual states, polarisability and selection rules. Pure rotational and vibrational-rotational Raman spectra. Polarisation of Raman transitions.

Title: Surface Science

Lecturer: Dr M Kadodwala

Aims: To serve as an introduction into surface science, to describe modern spectroscopic techniques of surface analysis and how they can be applied to model systems.

Objectives:

1. Understand why UHV techniques are necessary to study model systems.

2. Be fluent in the nomenclature of surface structure and to understand concepts such as surface relaxation and reconstruction.

3. Understand low energy electron diffraction and how it can be applied in the determination of surface structure.

4. Understand adsorption at surfaces, and the importance of physisorption and chemisorption.

5. Know why electron based spectroscopic techniques are employed in surface science and be familiar with those commonly used.

6. Understand the technique of temperature programmed desorption and its kinetics.

7. Know about vibrational spectroscopy at surfaces and their selection rules.

Outline:

What is surface science ?

Ultra high vacuum, single crystal surfaces, surface density.

Techniques generally, electron surface sensitivity.

Electron spectroscopy:

Energy distribution curves

Auger electron spectroscopy

X-ray photoelectron spectroscopy (chemical shifts, relaxation)

UV photoelectron spectroscopy.

General adsorption:

Physisorption

Chemisorption

Sticking probability

Langmuir and precursor state adsorption

Accommodation.

Thermal desorption spectroscopy:

Kinetics of desorption.

Surface Structure:

Nomenclature

2D Bravais lattices

Relaxation

Low Energy electron diffraction (LEED):

Electron diffraction

Ewald sphere construction.

Reconstruction

Matrix notation.

Vibrations at surfaces:

RAIRS, HREELS, SERS, SFG

Selection rules

Vibrational relaxation.

Title: Intermolecular Forces

Lecturer: Dr. J.H. Dymond

Aims: To introduce students to a quantitative representation of the forces that can

operate between molecules; to the method of interpretation of dilute gas

properties in terms of pair potential energy functions; to the many-body

problem; and to appreciate the importance of computer simulation techniques

in solving additional problems when treating dense systems.

Objectives:

1. explain how pVT data for gases, and the Joule-Thomson effect, each provide

evidence for molecular interactions

2. calculate the inversion temperature, Boyle temperature and the critical

constants for a van der Waals gas

3. describe the origins of intermolecular forces

4. give general expressions for the orientation energy, induction energy and dispersion energy between two molecules

5. describe the nature of the hydrogen bond

6. discuss repulsive forces

7. describe model pair potential energy functions

8. describe how information on U(R) can be obtained from second virial

coefficient and viscosity measurements; know how such measurements are

obtained, how values for molecular parameters can be derived, and what

information they give about the adequacy of U(R)

9. describe how molecular beam scattering and vacuum UV spectroscopy

provide information on U(R)

10. discuss the present state of knowledge of U(R) for atoms and molecules

11. explain the many-body problem as applied to dense gases, liquids and solids

12. describe the Molecular Dynamics and Monte Carlo simulation methods and

discuss their application in calculating properties for dense systems

Outline:

Introduction. Differences between properties of real gases and ideal gases. Origins of intermolecular forces. Model pair interaction potential energy functions. Determination of potential parameters from experimental dilute gas data. Dense gases, liquids and solids. The many-body problem. Application of Molecular Dynamics and Monte Carlo simulation methods.

Title: Surface Chemistry and Heterogeneous Catalysis

Lecturer: Dr D Lennon

Aims: To provide an introduction to the main concepts of heterogeneous catalysis through the study of the chemistry and kinetics of reactions occurring at the catalyst surface. Particular emphasis is given to the manufacture, characterization and testing of catalysts to demonstrate how catalysts can be designed for specific reactions.

Objectives:

1. Be able to derive the Langmuir isotherm for (a) the adsorption of a single substance at a solid surface and (b) the competitive adsorption of two gases at the same solid surface.

2. Appreciate the factors that are important for the design and preparation of supported catalysts.

3. Have knowledge of experimental methods used to characterise heterogeneous catalysts.

4. Understand the derivation of appropriate kinetic expressions for unimolecular and bimolecular surface-catalysed reactions and the use of kinetic measurements to determine reaction mechanisms.

5. Understand the Langmuir-Hinshelwood and Rideal Eley mechanisms with reference to alkenes and alkynes.

6. Understand the terms structure sensitive/insensitive, selectivity and stereospecificity in relation to catalytic processes.

Outline:

Introduction to the principles of heterogeneous catalysis by linking together concepts developed in earlier physical, inorganic and organic chemistry lectures; physical and chemical adsorption at the surface of a solid; interactions in supported metal/metal oxide catalysts; reference to the design of catalysts tailored to specific industrial processes; the preparation of supported metal/metal oxide catalysts exemplified both by model catalysts which are currently being developed in the laboratory and well characterised industrial catalysts; the use of surface science techniques, temperature programmed desorption and reduction, surface area determination and modern spectroscopic methods in the characterisation of catalysts; rates and kinetic modes of reactions exemplified by catalysed reactions used for large scale organic/inorganic synthesis and processes designed to provide a cleaner environment.

Title: Advanced Group Theory

Lecturer: Dr. rer. nat. L.Hecht

Aims: To further develop the group theoretical arguments presented in the third year lecture

course on molecular symmetry into more sophisticated concepts and demonstrate

valuable applications in atomic and molecular physics by means of worked examples.
Objectives:

1 Specify the characters of symmetrized and anti-symmetrized direct product

representations and apply them to the characterization of singlet and triplet states and

the Jahn-Teller effect.

2. Characterize double groups for molecular species with an odd number of electrons and

use the character tables of double groups to solve simple problems such as the

determination of spin-orbit and crystal field splitting schemes.

3. Define the time reversal operator in classical and quantum mechanics, state Kramers’

theorem and generalize the matrix element selection rule to cover time-even or time-

odd operators and even- or odd-electron states.
Outline:

Because it is essentially qualitative yet still mathematically rigorous, group theory is an excellent vehicle for physicists to employ when venturing into the chemistry jungle since molecules are usually too complicated for the application of detailed analytical physics. A central theme of this course is the proper treatment of degeneracies, which is glossed over in the third year molecular symmetry course.

Further development of the concept of direct products to include symmetrized and antisymmetrized direct product representations and their associated characters, determination of singlet and triplet states of transition metal complexes, group theoretical background to the Jahn-Teller effect.

Double finite point groups, specification of spin-orbit crystal field states.

Classical and quantum-mechanical versions of the time reversal operator, time-even and time-odd physical quantities, anti-unitary operators, Kramers’ theorem, general selection rule for matrix elements of even- and odd-electron systems with time-even and time-odd operators, time reversal operator for spin particles, time reversal and extra degeneracies, existence of permanent electric and magnetic dipole moments in degenerate states, Jahn-Teller effect in the presence of spin-degeneracy.

Title: Statistical Thermodynamics

Lecturer: Dr J. Dymond

Aims: To show how equilibrium thermodynamic property data for dilute gases and solids, and chemical reaction rates, can be related to properties of the individual molecules.

Objectives:

1. Derive the number of ways of distributing n indistinguishable particles among g degenerate energy states.

2. Give the corrected Boltzmann statistics for the total number of arrangements of N particles, where n_i are in energy level e_i which has a degeneracy g_i

3. State the Boltzmann distribution law, and use it to determine the relative populations of different energy levels.

4. Appreciate the meaning and importance of the molecular partition function, and relate it to the total energy of a system.

5. Factorise the molecular partition function

6. Give the expression for the translational partition function, and hence the contribution to the energy and heat capacity at constant volume for an ideal gas.

7. Give a statistical thermodynamic explanation for ideal gas expansion at constant temperature.

8. Appreciate the impossibility of obtaining absolute energies.

9. Give the expression for the rotational partition function, and know the meaning of the characteristic rotational temperature and the symmetry number.

10. Give the contribution to the energy and heat capacity at constant volume from rotational motion.

11. Give the expression for the vibrational partition function, and know the meaning of the characteristic vibrational temperature.

12. Calculate the contribution to the energy and heat capacity at constant volume arising from vibrational motion.

13. Describe ortho and para-states of diatomic molecules, and understand the alternating intensities to be found in rotational Raman spectra.

14. Calculate enthalpy changes for reactions.

15. Account for the temperature dependence of the heat capacities of solids.

16. Relate the Boltzmann expression for entropy to the classical entropy.

17. Give the statistical thermodynamic expression for entropy in terms of energy and the molecular partition function.

18. Give the Sackur-Tetrode equation, and demonstrate that the dependence of entropy for an ideal gas on T at constant V, and on V at constant T, agrees with classical results.

19. Explain what is meant by residual entropy, and calculate its values for certain systems.

20. Relate the Helmholtz and Gibbs energies to the molecular partition function.

21. Give approximate values for the translational, rotational, vibrational and electronic contributions to the molecular partition function.

22. Explain chemical equilibrium in terms of the distribution of molecules among energy levels, and hence understand the molecular factors that influence the position of equilibrium.

23. Describe transition state theory and derive and expression for absolute reaction rates.

24. Calculate steric factors for reactions involving molecules of differing complexity.

Outline:

This course is designed to show how equilibrium thermodynamic data for dilute gases and solids, and chemical reaction rates, depend upon the properties of the constituent molecules.

Introduction - derivation of the numbers of ways of distributing indistinguishable particles among degenerate energy levels, corrected Boltzmann statistics and simple applications; the molecular partition function (q); dependence of the internal energy on q; factorisation of q; the contribution from translational motion, and translational energy; absolute energies; rotational partition functions and the symmetry number; rotational energy and heat capacity contribution; vibrational partition function, the characteristic vibrational temperature and the contribution to the heat capacity; electronic partition function; effects of nuclear spin - ortho and para forms; relative intensities of rotational Raman spectra; enthalpy changes for chemical reactions; classical and statistical entropies.

Sackur-Tetrode equation for monatomics; residual entropy for simple diatomics and gases; free energy changes; chemical equilibrium; simple collision theory of reaction rates; activated complex theory, and examples.

Title: Chirality

Lecturer: Dr R D Peacock

Aims: The aims of the course are to provide an introduction to the occurrence and importance of chirality; to explain how chiral molecules may be detected, resolved or synthesised and to give an appreciation of circular dichroism spectroscopy and its use in determining the absolute configuration of chiral molecules.

Objectives:

1. Understand the basic definitions of chirality - enantiomer, diasterioisomer, racemate. Have an appreciation of the importance of chirality in the interaction of chiral molecules with natural systems such as man.

2. Appreciate the idea of a chromophore. Know the common types of chromophore and the transitions which they undergo.

3. Understand the concept of the polarisation of an electronic transition, of plane polarised light and of plane polarised absorption spectroscopy. Understand how the polarisation of a transition can be derived by multiplying the phase of the HOMO with that of the LUMO (or higher unoccupied molecular orbital).

4. Be able to use phase multiplication to determine the polarisations of the p -> p * transition of ethene and the d -> d * transition of the Mo2 chromophore and appreciate how the method can be used to determine the polarisation (long or short axis) of the transitions of polyacenes such as substituted benzenes, naphthalene and anthracene.

5. Understand how in the twisted Mo2 chromophore there is a transient helical charge distribution during the d -> d * transition and how this charge distribution interacts differently with left and right circularly polarised light leading to circular dichroism. Appreciate how the sense of twist of the chromophore (and hence the absolute configuration) is related to the sign of the CD spectrum.

6. Understand the concept of chirally coupled (organic) chromophores. Understand how the CD spectrum of such a system is related to the chirality of the molecule. Be able to determine the chirality of a pair of coupled chromophores from the sign of its CD spectrum.

7. Understand how enantiomers can interact in homochiral or heterochiral pairs of stacks. Appreciate the molecular basis of diastereomeric interactions ("three point model").

8. Know the common methods of resolving chiral molecules.

9. Be able to describe, and appreciate the molecular basis of, the various methods of detecting chiral molecules - chiral chromatography, chiral NMR reagents, chiral sensors.

10. Appreciate the molecular basis of asymmetric catalysis - particularly as applied to the examples given in lectures.

Outline:

General definitions of chirality etc.; chromophores; polarisation of electronic transitions; the alkene and dimolybdenum chromophores; twisted chromophores and circular dichroism; coupled chromophores - bianthryls etc, use in determining absolute configuration; diasteriomeric interactions; resolution of enantiomers; chiral GLC, chiral HPLC, chiral NMR shift reagents, chiral sensors; asymmetric catalysis.

Title: Laser Spectroscopy

Lecturer: Dr J K Tyler

Aims: This course is intended to introduce the principles of laser operation in general and the details of specific devices. Some important applications of lasers in chemistry and spectroscopy are touched on.

Objectives:

1. The nature of radiative transitions and basic laser theory.

2. Ways of achieving population inversions.

3. Optical gain and feedback, and the criteria for pulsed and continuous operation.

4. Rare gas discharge lasers, molecular infrared gas lasers, hydrogen halide chemical lasers and organic dye solution lasers.

5. Diode lasers.

6. Excimer lasers and super-radiance.

7. The laser as a spectroscopic source and as an excitation source for Raman spectroscopy.

8. Flash photolysis with lasers.

9. Multiphoton processes and infrared photochemistry.

Outline:

Radiative and non-radiative energy changes. Spontaneous and stimulated radiative processes and basic laser theory. Practical realisation of laser action. Population inversion. The ammonia maser. Optical gain and feedback. The ruby and neodymiun ion lasers. Criteria for pulsed and continuous operation. Rare gas discharge lasers. Details of the He/Ne device. Molecular gas lasers operating in the infrared region exemplified by the CO₂/N₂ system. Hydrogen halide chemical lasers. Organic dye solution lasers.

Semiconductor levels and diode lasers. The N₂ laser. Super-radiance. Excimer and exciplex lasers. The nature of laser radiation. The laser as a spectroscopic source. Tunability. The laser as an excitation source for Raman spectroscopy. Flash photolysis with lasers. Multiphoton processes. Infrared photochemistry. Laser separation of isotopes.

Title: Solid State Chemistry : Materials and Microstructure

Lecturer(s): Dr D McComb

Aims: To further advance understanding of the inter-relationship between the structure and the properties of materials.

Objectives: At the end of the course students will have a knowledge of the following topics,

1. Review of point defects and ionic conductivity

2. Properties and applications of fast-ion conductors

3. Non-stoichiometric compounds : structure and electronic properties

4. Dislocations and plastic deformation in metals : their influence on mechanical properties

5. Techniques for investigation of local structural environments

6. At the end of the course students should be able to describe the properties of a material in terms of the fundamental aspects of solid state chemistry.

Outline: Further development of the influence of point defects on the properties of materials. The thermodynamics of formation of point defects as well as the properties/ applications of ionic conductors and solid electrolytes will be studied. The structure-property relationships that result in fast-ion conductors will be considered using appropriate examples. The chemical view regarding the influence of extended defects (dislocations & grain boundaries) on the mechanical properties of materials will be developed. In particular, the relationship between slip planes and dislocations will be developed and the plastic deformation behaviour will be considered. For all the objectives examples from recent research literature will be used to illustrate the increasing importance of structure-property relationships in modern solid-state chemistry.

Title: Modern Molecular Calculations

Lecturer(s): Dr B C Webster

Aims: The aims of the course are to introduce the computer based methods which are available for the ab-initio and semi-empirical calculation of molecular properties and to review and develop some of the concepts which were introduced in third year courses in quantum mechanics and bonding theory.

Objectives:

1. Appreciate the need for and the validity of approximate calculations and relate them to the approximations inherent in measurement.

2. Appreciate calculation strategies on large computers without becoming involved in the details of the programming.

3. Approach with a more critical attitude results obtained from the use of large established computer programs.

4. Describe the general structure of calculations of Hartree Fock/Self Consistent Field (HF/SCF) wavefunctions.

5. Describe the various approximations involved in HF/SCF calculations.

6. Describe what is meant by a minimal basis set and an extended basis set and describe various commonly used basis sets of Gaussian functions matched to Slater type orbitals: STO-3G, 3-21G, 3-21G(*), 6-21G, 6-31G*, 6-31G**.

7. Explain why the number of basis functions used in a calculation is limited by available computing time.

8. Describe how molecular geometry can be optimised.

9. Describe the effects of neglecting electron correlation.

10. Describe the general structure of calculations of configuration interaction (CI) calculations.

11. Describe the various approximations involved in CI calculations.

12. Explain the need to use limited CI methods to reduce computer time.

13. Describe the trade-off between accuracy of calculation and computing time and how this is related to molecular size.

14. Explain why ab-initio methods cannot at present be applied to very large molecules and the need for semi-empirical methods.

15. Describe the basis of the main types of semi-empirical methods: NDDO, INDO and CNDO including the main approximations made and the major variants.

16. Explain the value of parameterisation in semi-empirical methods.

17. Assess the likely accuracy of properties such as equilibrium geometries, vibrational frequencies, absolute entropies, barriers to internal rotation and inversion, electronic dipole moments and bond dissociation energies calculated using ab-initio and semi-empirical methods.

18. Describe the Born-Oppenheimer approximation and its effect.

19. Write the molecular Hamiltonian operator in atomic units within the Born-Oppenheimer approximation for any molecule.

20. State the requirements for a satisfactory electron wavefunction.

21. Describe the relationship of Slater-type orbitals and Gaussian-type atomic functions to hydrogenic wavefunctions.

Outline:

Revision of some quantum mechanical concepts. The HARTREE-FOCK-ROOTHAAN method. Basis sets. Strategies for solution of HFR equations. Electron correlation. Semi-empirical techniques.