Table Of ContentFrontiers of Laser Spectroscopy of Gases
NATO ASI Series
Advanced Science Institutes Series
A Series presenting the results of activities sponsored by the NA TO Science Committee,
which aims at the dissemination of advanced scientific and technological knowledge,
with a view to strengthening links between scientific communities.
The Series is published by an international board of publishers in conjunction with
the NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical Kluwer Academic Publishers
and Physical Sciences Dordrecht, Boston and London
0 Behavioural and Social Sciences
E Applied Sciences
F Computer and Systems Sciences Springer-Verlag
G Ecological Sciences Berlin, Heidelberg, New York, London,
H Cell Biology Paris and Tokyo
Series C: Mathematical and Physical Sciences -Vol. 234
Frontiers of Laser
Spectroscopy of Gases
edited by
Antonio C. P. Alves
University of Coimbra, Portugal
John M. Brown
University of Oxford, UK
and
J. Michael Hollas
University of Reading, U.K.
Kluwer Academic Publishers
Dordrecht / Boston / London
Published in cooperation with NATO Scientific Affairs Division
Proceedings of the NATO Advanced Study Institute on
Frontiers of Laser Spectroscopy of Gases
Vimeiro, Portugal
30 March - 10 April 1987
Library of Congress Cataloging in Publication Data
Frontiers of laser spectroscopy of gases / edited by A.C.P. Alves.
J.M. Brown. and J.M. Hollas.
p. crn. -- (NATO ASI series. Series C. Mathematical and
physical sciences; vol. 234)
·Contains the lectures presented at the NATO Advanced Study
Institute on 'Frontiers of Laser Spectroscopy of Gases' held in the
Hotel Golf Mar. Vimeiro. near Torres Vedras. Portugal. from 30 March
to 10 April 1987"--Pref.
"Publ ished in cooperation with NATO Scientific Affalrs Divislon."
Includes index.
ISBN-13: 978-94-010-7849-8 e-ISBN-13: 978-94-009-3003-2
001: 10.1007/ 978-94-009-3003-2
~. ;"ass, spactroscopy--Con~resses. I. Alves. A. C. P.
II. Brown. J. M. III. Hollas. J. Michael (John Michael) IV. NATO
Advanced Study Institute on ."Frontiers of Laser Spectroscopy of
Gases· (1987 Vlmeiro. Lisbon. Portugal) V. North Atlantic Treaty
Organlzation. Scientific Affairs Dlvislon. VI. Series: NATO ASI
series. Series C. Mathematical and physical sciences; no. 234.
OC454.L3F76 1988
535.5'8--dc19 88-12042
CIP
ISBN-13: 978-94-010-7849-8
Published by Kluwer Academic Publishers,
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All Rights Reserved
© 1988 by Kluwer Academic Publishers
Softcover reprint of the hardcover 1st edition 1988
No part of the material protected by this copyright notice may be reproduced or utilized
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copyright owner.
CONTENTS
Preface ix
Emeritus Professor Fernando Pinto Coelho xi
Directors xiii
Contributors
XVI. I.
SPECTROSCOPY WITHOUT LASERS, D.A. RAMSAY
Introduction 1
Electronic Spectra 3
Comparison of Classical and Laser Techniques 5
Philosophical Remarks 7
INFRARED LASERS FOR SPECTROSCOPY, W. URBAN
Survey of Lasers, Suitable for Spectroscopy in the Medium
Infrared 9
The Colour Centre Laser 21
The Carbon Monoxide Laser 29
TUNABLE FAR INFRARED LASER SPECTROSCOPY, K.M. EVENSON,
D.A. JENNINGS, AND M.D. VANEK
Introduction 43
Second Order Spectrometer 44
Third Order Spectrometer 44
Experimental Technique 47
Results 47
Conclusion 48
GENERATION OF COHERENT TUNABLE RADIATION, R. WALLENSTEIN
Introduction 53
Dye Lasers 53
Generation of Tunable UV and IR 54
Tunable VUV and XUV Radiation Generated by Frequency
Mixing in Gases 55
Third-Order Frequency Conversion 55
Fifth-Order Frequency Mixing 57
Applications 58
VI
TUNABLE COHERENT SOURCES FOR VACUUM ULTRAVIOLET SPECTROSCOPY,
B.P. STOICHEFF
Introduction 63
Stimulated Raman Scattering 64
Harmonic Generation and Frequency Mixing 67
Applications in Spectroscopy 75
Conclusions 86
THE FREE ELECTRON LASER, OFFSPRING OF SYNCHROTRON RADIATION,
S. LEACH
Introduction 89
Synchrotron Radiation 92
Insertion Devices 98
Harmonic Generation 111
Free Electron Laser 118
Electron Accelerators 134
Free Electron Laser Facilities 135
Summary of FEL Properties and Applications 141
LASER DOPPLER-FREE TECHNIQUES IN SPECTROSCOPY, B. CAGNAC
In Radiofrequency Domain 153
In Optical Domain 162
Applications of Two-Photon Spectroscopy. 176
ATOMIC LASER SPECTROSCOPY, P.E.G. BAIRD
Laser Spectroscopy of Fundamental Systems 187
Atomic Beams, Laser Cooling, Atomic Traps and Rydberg Atoms 204
Optical Rotation Produced by Atoms 217
LASER RAMAN SPECTROSCOPY, L.D. BARRON
Introduction 241
Theory of Linear Raman Processes 248
Some New Aspects of Linear Gas Phase Raman Spectroscopy 258
Theory of Nonlinear Raman Processes 263
Coherent Raman Spectroscopy 269
TECHNIQUES IN MOLECULAR LASER SPECTROSCOPY, R.N. DIXON
Introduction 281
Laser Stark Spectroscopy 282
Laser Magnetic Resonance 291
Laser Induced Fluorescence 295
Double Resonance Spectroscopy 301
vii
MULTIPHOTON IONIZATION SPECTROSCOPY WITH PHOTOELEGTRON
AND MASS SPECTRAL ANALYSIS, S.D. COLSON
Introduction 309
Multiphoton Ionization Photoelectron Spectroscopy 311
Multiphoton Ionization Mass Spectroscopy 314
Preparation of Free Radicals in Molecular Beams 314
Applications of Laser Ionization Mass and Photoelectron
Spectroscopy 316
Summary 323
MULTIPHOTON IONIZATION MASS SPECTROMETRY OF BIOMOLECULES,
J. GROTEMEYER AND E.W. SCHLAG
Introduction 325
Method 326
Results 331
Conclusion 342
UNIMOLECULAR DECAY OF ENERGY-SELECTED POLYATOMIC MOLECULAR
IONS BY RESONANCE-ENHANCED MULTIPHOTON IONIZATION IN A
REFLECTRON MASS SPECTROMETER, A. KIERMEIER, H. KUHLElHND,
H.J. NEUSSER, AND E.W. SCHLAG
Introduction 345
Photoelectron Kinetic Energy Analysis 346
Unimolecular Ion Decay in a Reflectron Time-of-Flight
Mass Spectrometer 347
Conclusion 351
INFRARED SPECTROSCOPY OF HOLECULAR IONS, T. OKA
Production of Holecular Ions 353
Infrared Spectroscopy of Molecular Ions using Frequency
Tunable Laser Sources 365
DYNAMICS OF THE PHOTODISSOCIATION OF SMALL MOLECULES,
P. ANDRESEN
Introduction 379
Experimental Techniques to Analyse Product Hotion 380
Photodissociation of H20 in the First Absorption Band 384
Weak and Strong Final State Interaction 394
Conclusions 417
viii
LASER SPECTROSCOPY OF CHEMICAL INTERMEDIATES IN SUPERSONIC
FREE JET EXPANSIONS, S.C. FOSTER, R.A. KENNEDY, AND
T.A. MILLER
Introduction 421
Supersonic Free Jet Expansions 423
Spectroscopy of Ions 430
Neutral Free Radicals 438
Sununary 447
THE INFRARED SPECTROSCOPY OF THE H+ fu~D HD+ MOLECULAR IONS
AT THEIR DISSOCIATION LIMITS, A.3CARRINGTON, I.R. McNAB,
AND C.A. MONTGOMERIE
+
The Spectroscopy of HH1+ 451
The Spectroscopy of D 456
THE INTERPRETATION OF VIBRATIONAL OVERTONE SPECTRA OBSERVED
BY FOURIER TRANSFORM AND LASER PHOTOACOUSTIC SPECTROSCOPY,
I.M. MILLS
Experimental Techniques 461
Anharmonicity in a Diatomic Molecule 462
A Simple Classical Model 464
A Simple Quantum Mechanical Model 466
Vibrational Band Intensities 475
Effects of Fermi Resonance, and Results on Dichloromethane 476
Nickel Tetracarbonyl 482
Discussion 482
INTERSTELLAR MASERS AND STAR FORMATION IN THE GALAXY,
G. WINNEWISSER
Introduction 491
Historical Notes 492
Interstellar Molecular Spectroscopy 495
Interstellar Masers 498
Future Perspectives 507
Index 509
PREFACE
This volume contains the lectures presented at the NATO Advanced Study
Institute on "Frontiers of Laser Spectroscopy of Gases" held in the
Hotel Golf Mar, Vimeiro, near Torres Vedras, Portugal from 30 March to
10 April 1987. The objective of the meeting was to take stock of the
recent technological developments involving lasers and to assess their
impact on spectroscopy. The whole range of wavelengths from the far
infrared through to the extreme ultraviolet was covered. In addition,
specific applications to both atoms and molecules were described.
Indeed, one of the most successful and pleasant aspects of the Institute
was the joint participation of atomic physicists and molecular spectro
scopists, who meet all too rarely these days. The Institute also
succeeded in covering a wide time span from the very earliest days of
lasers to some of the very latest developments in both lasers and their
applications to spectroscopy.
There were 14 invited lecturers, giving a total of 40 lectures, and
89 other participants at the Institute. Each of the invited lecturers
has contributed a chapter to this volume. In addition, on Thursday 2nd
April a special one-day session was held in the Chemistry Department at
the University of Coimbra to mark the retirement of Professor Dr. F.
Pinto-Coelho. Three speakers, Professors Carrington, Mills and
Winnewisser, gave excellent talks on this occasion and these are also
reproduced as chapters in this volume. The Institute was fortunate in
the participation of Dr K. M. Evenson, one of the pioneers of far
infrared spectroscopy. He was persuaded to make a presentation on
developments in this area and has also contributed a chapter.
All who were present at the A.S.I. can testify to its successful
outcome. This was fuelled by the enthusiasm for the subject matter of
all the participants, both young and old, and was helped in no small
way by a fine setting for the meeting on the cliffs overlooking the
Atlantic Ocean. The Portuguese were warm and generous hosts and the
one-day visit to the lovely mediaeval city of Coimbra was particularly
memorable.
It is a pleasure to express our thanks to the NATO Scientific
Affairs Division, whose financial support made this Institute possible.
In addition, we have received generous contributions from the following
companies and institutions:
Imperial Chemical Industries
Unilever
Spectra-Physics
Newport Corporation
Burleigh Instruments
U.S. Air Force
U.S. Army
U.S. Office of Naval Research
IX
x
Junta Nacional de Investiga9ao Cientifica e Tecno16gica
Instituto Nacional de Investiga~ao Cientifica
Fundarao Calouste Gulbenkian
INVOTAN-Portugal
Secretaria do Estado do Ensino Superior Reitoria da Universidade de
Coimbra
and also support from:
Banco Pinto e Sotto Mayor
Banco Portugues do Atlantico
Regiao de Turismo do Oeste
We are very grateful to all of these for their help in making the A.S.I.
such a success both scientifically and otherwise.
A.C.P. Alves
J.H. Brown
J .H. Hollas
