Molecular Spectroscopy Volume 2

594 Pages·1974·28.734 MB·English

by  et al

A Specialist Periodical Report
Molecular Spectroscopy
Volume 2
A Review of the Literature published during
1972 and early 1973
Senior Reporters
R. F. Barrow, Physical Chemistry Laboratory, University
of Oxford
D. A. Long, School of Chemistry, University of Bradford
D. J. Millen, Department of Chemistry, University College,
London
Reporters
R. T. Bailey, University of Strathclyde
J. Behringer, University of Munich, West Germany
M. S. Child, University of Oxford
F. R. Cruickshank, Univebsity of Strafhclyde
R. E. Hester, University of York
J. W. Johns, National Research Council of Canada, Ottawa,
Ontario, Canada
A. C. Legon, University College, London
E. A. Mallia, University of Oxford
W. B. Person, University of Florida, USA.
D. Steele, Royal Holloway College, University of London
@ Copyright 1974
The Chemical Society
Burlington House, London, WIV OBN
ISBN: 0 85186 516 X
Library of Congress Catalog Card No. 72-92545
Printed in Great Britain by
Billing 6 Sons Limited, Guildford and London
Foreword
This is the second of a series of annual volumes dealing with molecular
spectroscopy : that is microwave spectroscopy, electronic spectroscopy, and
infrared and Raman sp~iii~~~cAosp yw.e explained in the Foreword to the
first volume, the sheer iditine of the literature relating to this extensive
subject, makes it quite mipracticable to attempt, annually, a complete
coverage of all aspects ot molecular spectroscopy. Our policy, therefore,
has been to select those areas of molecular spectroscopy whose review we
consider would be particularly timely and interesting. The topics chosen can
then be given a detailed and critical analysis so that the reviews present not
only a condensate of the literature but also set the subject in perspective.
With these objectives in mind the literature for a number of the topics dealt
with in this volume has been reviewed over a period of several years.
We are pleased to record our thanks again to our Reporters and the
Editorial Staff of The Chemical Society for their assistance and collaboration
in the preparation of this volume,
R.F.B.
D.A.L.
D.J.M.
March 1974

Contents
Chapter 1 Microwave Spectroscopy 1
By A. C. Legon and D. J. Millen
1 Diatomic Molecules 1
2 Triatomic Molecules 3
3 Inorganic Molecules 7
4 Organic Molecules 20
Acyclic Molecules without Internal Rotation 20
Acyclic Molecules with Internal Rotation 40
Hydrocarbons and Halogeno-derivatives 40
Alcohols 42
0t her Molecules 43
Experimental Evaluation and Theoretical Calculation
of Barriers 45
5 Cyclic Molecules 46
Three-membered Rings 46
Four-membered Rings 51
Five-membered Rings 53
Six-membered Rings 61
Fused Rings 67
6 Molecules in States other than lC 74
7 Analysis of Spectra and the Evaluation of Molecular
Parameters 76
8 Vibrati on-Rotat ion Interacti on 78
9 Linewidths, Lineshapes, and Pressure Broadening 84
10 Double Resonance 87
11 Astrophysics 93
12 Instrumentation 96
13 Analytical Applications 98
vi Contents
Chapter 2 Theories of Resonance Raman Scattering 100
By J. Behringer
1 Introduction 100
2 The Relation of Resonance Raman Scattering to
Resonance Fluorescence 101
3 Classical Theories of the Vibrational Resonance Raman
Effect 109
A The Polarizability Theory and its Limitations 110
B Amplitude and Phase Modulation of the
Polarizability 118
C Fourier Expansion of the Polarizability 123
D The Method of Parametrically Excited Electronic
Oscillations 125
E The Distinction of Scattering and Fluorescence
by Classical Theory 128
4 Quantum Mechanical Theories of the Resonance
Raman Effect: General Aspects 131
A Basic Methods for the Description of Two-
photon Processes 131
B Inclusion of Damping 138
C Specification of States 14 0
D Resonance Raman Effect and Resonance
Fluorescence 143
E Electric Dipole and Higher Approximations of
the Interaction Hamiltonian 145
F Phase Correlations 146
5 Quantum Mechanical Theories of the Resonance
Raman Effect: Special Systems 146
A Atoms and Mononuclear Ions 147
Free Atoms 148
Atoms Influenced by Fields 153
B Molecules and Polynuclear Ions 154
Vibrational Resonance Raman Eff'ect 155
Generalities 155
Diatomic molecules 157
Polyatomic molecules 164
Rotational Resonance Raman Eff'ect 167
C Condensed Systems 168
Contents vii
Chapter 3 Infrared and Raman Studies of Molecular Motion 173
By R. T. Bailey
1 Introduction 173
2 Background Molecular Theory i74
Correlation Function Approach 174
Infrared Absorption 176
Raman Scattering 180
The Calculation of Correlation Functions 184
Models of Molecular Motion 188
Molecular Dynamics Calculations 200
Relationsh ip bet ween some Correia t ion Functions 204
Moment Analysis 206
3 Experimental Techniques 210
Infrared Absorption 210
Bandshape Measurements 210
Computation of Dipole Correlation Functions 21 1
Raman Scattering 212
Bandshape Measurements 212
4 Applications 21 4
Infrared Studies 214
Gaseous Phase 215
Condensed Phase 219
Raman Studies 232
Gaseous Phase 233
Condensed Phase 234
Low-frequency Studies 249
Far-infrared Studies 250
Low-frequency Raman Studies 257
5 Summary 26 I
Chapter 4 Infrared Fluorescence Studies 262
By R. T. Bailey and F. R. Cruickshank
1 Introduction 262
2 Experimental Techniques 264
Laser Sources 264
Helium-Neon 264
Carbon Dioxide 264
Chemical Lasers 270
Contents
Tunable Lasers 27 1
Solid-state Lasers 276
Detectors 276
Quant um Detectors 278
Lead sulphide, PbS 280
Indian antimonide, InSb 280
Mercury cadmium telluride, Hg,-,Cd,Te 280
Gold-doped germanium 280
Mercury-doped germanium 282
Copper-doped germanium 282
Photon-drag Detectors 282
Fluorescence Measurements 283
CW Measurements 28 3
Pulsed Measurements 286
Double-resonance Techniques 290
Stimulated-Raman Pumping 29 1
Matrix-isolation Studies 293
3 Theory of Vibrational Energy Transfer 294
Introduction 294
Theoretical Prediction of Transition Probability 294
Extraction of Rate Constants from Fluorescence-
decay Curves 299
Extraction of Transition Probability from Experi-
mental Rate Constants 300
Summary 303
4 Experimental Measurements of the Hydrogen Halides 304
Hydrogen Fluoride 304
The Kinetic Model and V T Transfer 304
--f
V -+ V Transfer 305
V + V Transfer to Other Gases from HF and DF 308
Hydrogen and Deuterium Chlorides 309
The Kinetic Model and V + (T,R) Energy Transfer 309
V + V Transfer 3 10
V V Transfer to Foreign Gases 31 1
--+
Hydrogen Bromide 3 14
V + (T,R) Transfer and the Kinetic Model 314
V V Transfer 314
--f
V -+ V Transfer from HBr to Foreign Gases 314
Hydrogen Iodide 315
V -+( T,R) Transfer 315
Summary 315
5 Experimental Measurements of Methyl Halides 317
Methyl Fluoride 317