Table Of Content6
Springer Series in Chemical Physics
Edited by Fritz Peter Schafer
"-------------'
Springer Series in Chemical Physics
Editors: V. I. Goldanskii R. Gomer F. P. Schafer 1. P. Toennies
Volume 1 Atomic Spectra and Radiative Transitions
By I. I. Sobelman
Volume 2 Surface Crystallography by LEED Theory, Computation
and Structural Results
By M. A. Van Hove, S. Y. Tong
Volume 3 Advances in Laser Chemistry
Editor: A. H. Zewail
Volume 4 Picosecond Phenomena
Editors: C. V. Shank, E. P. Ippen, S. L. Shapiro
Volume 5 Laser Spectroscopy Fundamentals and Techniques
By W. Demtroder
Volume 6 Laser-Induced Processes in Molecules Physics and Chemistry
Editors: K. L. Kompa, S. D. Smith
Volume 7 Excitation of Atoms and Broadening of Spectral Lines
By I. I. Sobelman, L. A. Vainshtein, E. A. Yukov
Laser-Induced Processes
in Molecules
Physics and Chemistry
Proceedings of the European Physical Society
Divisional Conference at Heriot -Watt University
Edinburgh, Scotland, September 20-22, 1978
Editors
K.L.Kompa and S.D. Smith
With 196 Figures
Springer-Verlag Berlin Heidelberg New York 1979
Professor Dr. Karl Ludwig Kompa
Projektgruppeflir Laserforschung, Max-Planck-GeseIlschaft zur Forderung der Wissenschaften e.V.
D-8046 Garching bei Miinchen, Fed. Rep. of Germany
Professor Stanley Desmond Smith, Ph.D. D.Sc. FRS
Department of Physics, Heriot-Watt University, Riccarton,
Edinburgh EH14 4AS, Scotland
Series Editors:
Professor Vitalii I. Goldanskii Professor Dr. Fritz Peter Schafer
Institute of Chemical Physics, Academy Max-Planck-Institut flir Biophysikalische
of Sciences, Vorobyevskoye Chaussee 2-b Chemie, D-3400 Gottingen-Nikolausberg
Moscow V-334, USSR Fed. Rep. of Germany
Professor Robert Gomer Professor Dr. J. Peter Toennies
The James Franck Institute Max-Planck-Institut flir Stromungsforschung
The University of Chicago, 5640 Ellis Av enue BottingerstraBe 6-8
Chicago, IL 60637, USA D-3400 Gottingen, Fed. Rep. of Germany
Conference Chairmen: Professor S. D. Smith FRS and Professor K. L. Kompa
Conference Organizer: Dr. R.G. Harrison, Heriot-Watt University
Conference Treasurer: H.A. MacKenzie, Heriot-Watt University
Sponsors: Imperial Chemical Industries Ltd.; Spectra Physics Inc.;
Edinburgh Instruments Ltd.
Programme and Advisory Committee: M.J. Berry, B. Bolger, B. Burlamacchi, J. Ernest,
S. Kimel, K.L. Kompa, S. Leach, V.S. Letokhov, S.D. Smith,
I.J. Spalding, O. Svelto, J.J. Turner, H. Walther, R.N. Zare
ISBN-I3: 978-3-642-67256-9 e-ISBN-I3: 978-3-642-67254-5
DOl: 10.1007/978-3-642-67254-5
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is
concerned, specifically those of translation, reprinting, reuse of illustrations, broadcasting, reproduction by
photocopying machine or similar means, and storage in data banks. Under § 54 of the German Copyright
Law where copies are made for other than private use, a fee is payable to the publisher, the amount of the
fee to be determined by agreement with the publisher.
© by Springer-Verlag Berlin Heidelberg 1979
Softcover reprint of the harcover I st edition 1979
The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a
specific statement, that such names are exempt from the relevant protective laws and regulations and
therefore free for general use.
Preface
This conference on both the physics and chemistry of laser-induced processes
in molecules was organized by the Quantum Electronics Divisional Board of
the European Physical Society whose membership is given on p.367. The confer
ence aim, to mix physicists and chemists interested in this exciting field
both from Europe and further afield, was well fulfilled by the attendance
of around 250 participants and the submission of about 100 papers, which dre
presented here.
Numerous people at both the Physics Department, Heriot-Watt University,
Edinburgh, and at the Projektgruppe fUr Laserforschung, MPI, Garching, con
tributed hard work to the organization; in addition to Dr. Bob Harrison,
who bore the biggest burden with conspicuous success, we particularly thank
Hugh MacKenzie, Richard Dennis and last but not least Miss Joanne Askham and
the secretaries in Edinburgh together with Frau Doris Maischberger and the
secretaries in Garching.
December 1978 K.L. Kompa S.D. Smith
Conren~
Part I. Study of Lasers and Related Techniques Suitable for Applications
in Chemistry and Spectroscopy
Rare Gas Halogen Lasers and Photochemical Applications.
By S.D. Rockwood................................................... 3
Group VI Molecular Photolytic Dissociation Studies Using Rare Gas
Halide Lasers. By M.C. Gower, A.J. Kearsley, and C.E. Webb ......... 8
Broadly Tunable UV Source Based on Stimulated Raman Scattering.
By V. Wi 1k e and W. Schmi dt ......................................... 12
Laser-Induced Intermolecular and Intramolecular Energy Transfer
Processes. By S. Spei ser ........................................... 15
A New Method for Exposing Mammalian Cells to Intense Laser Radiation
Using the Evanescent Fields Created in Optical Waveguides.
By H.L. Cox, Jr. .................................................. 19
Time-Dependent Kinetic-Thermodynamic Description of a Nonequilibrium
Molecular System: The HF Chemical Laser. By A. Ben-Shaul, O. Kafri,
and R.D. Levine.................................................... 22
Low-Temperature Performance of Roto-Vibrational Molecular Lasers.
By J.M. Green...................................................... 26
HBr Laser Emission at 4 Based on the Chemical Generation of
~m
Bromine Atoms. By S.J. Arnold and K.D. Foster " .................... 29
Tunable Infrared Generation from Four-Wave Mixing in Room-Temperature
Germanium. By S.R. Butcher, R.G. Harrison, and R.A. Wood ........... 32
Part II. Spectroscopic Studies with and Related to Lasers
High-Resolution Double-Resonance Spectroscopy of SF6.
By P.F. Moulton and A. Mooradian ................................... 37
VII
High-Resolution Coherent Raman Spectroscopy of Methane and Intensity
of CARS vs Pressure in Gases. By J. -P. Boqui 11 on ................... 43
Molecular Spectroscopy of NO and C2H4 Using Step-Tunable IR Lasers
and the External Resonator Controlled Spin-Flip Raman Laser.
By G. Crowder, R.B. Dennis, H.A. MacKenzie, M.H. Mozolowski,
and M. Sioudi ...................................................... 46
Photophysics of Gaseous UF6 in the UV: Energy Ba'lance Through
Quantum Efficiency Measurements. By O. de Witte, R. Dumanchin,
J.P. Gauyacq, and M. Michon ........................................ 49
Optical Dephasing in Molecular Iodine. By R.G. Brewer and
S.S. Kano .......................................................... 54
An Efficient Algorithm for the Study of Nonlinear Resonant
Propagation of Two Concomitant Optical Pulses Interacting with
a Three-Level Atomic System. By F.P. Mattar and J.H. Eberly ........ 61
The Influence of Hyperfine Coherence and of Elastic Collisions on
the Circular Polarisation of Emission from Li2. By M.D. Rowe and
A.J. McCaffery..................................................... 66
Collisional Depolarization and Rotational Energy Transfer of the
7Li2B1rru - Li2S1/2 System Using Laser-Induced Fluorescene.
By C.R. Vidal ...................................................... 69
Saturated Absorption Experiments on a Molecule Dressed by a Radio-
frequency Fi e 1d . By E. Ari mondo and P. Glori eux .................... 71
dc Magnetic Field Effects on Polarized Monochromatic Laser Radiation
Absorption in Electronic Transitions: A Simple Model.
By M. Bernardini, A. Fubini, and G. Sacerdoti ...................... 74
Effect of Two-Photon Saturation on Ordinary Raman Scattering.
By A.D. Wilson-Gordon and H. Friedmann 78
Predissociation in the A'A" State of HNO.
By R.N. Dixon and M. Noble......................................... 81
Photoassociation of Heavy Metal Excimers: Spectroscopic,
Kinetic, and Laser Applications. By D.J. Ehrlich and
R. M. Osgood, Jr. ................................................... 85
Dye-Laser-Induced Emission from the KXe Molecule. By C.R. Webster and
F. Rostas .......................................................... 89
VIII
Laser-Induced Emission from the NaK Molecule in a Supersonic Beam.
By E.-J. Breford and F. Engelke .................................... 92
The Singlet-Triplet Energy Separation of CH2 and Spectroscopy of the
alAI State. By D. Feldmann, K. Meier, R. Schmiedl, H. Zacharias,
and K.H. Welge..................................................... 95
Time-Resolved Fluorescence Spectroscopy Using Pulsed Laser Excitation.
By K.P. Ghiggino, A.J. Roberts, and D. Phillips .................... 98
Ultrafast Spectroscopy with a Streak Camera: Excited State Spectros-
copy and Kinetics of Coumarin Derivatives. By J. Schulz-Hennig
and A. MUller ...................................................... 101
Laser-Induced Processes in Phthalocyanines. By J. McVie, R.S. Sinclair,
and T. G. Truscott .................................................. 104
Fluorescence Decay-Time Measurement of Rhodamine 6G and Rhodamine B
in Different Solutions. By H. Alobaidi, F. Alberkdar, Z. Hafidh,
and S. Alalkawy .................................................... 108
Laser Flash Spectroscopy of 4-Nitrostilbenes and Thioindigo Dyes;
Configuration of the Triplet State in Solution. By H. Garner and
D. Schulte-Frohl inde ............................................... 111
Part III. Multiphoton Excitation, Dissociation and Ionization
Laser-Induced Unimolecular Reactions. By N. Bloembergen and
E. Yablonovitch .................................................... 117
Time and Intensity Dependence of the Infrared Absorption of SF6:
Measurements with an Injection-Locked Single Mode TEA CO2 Laser.
By S.D. Smith, W.E. Schmid, F.M.G. Tablas, and K.L. Kompa .......... 121
IR Absorption of Highly Excited SF6.
By W. Fui3 and J. Hartmann .......................................... 128
Absorption of Intense Laser Radiation by SF6 and S2F10'
By J.L. Lyman ...................................................... 131
Collisional Effects in the Multiple-Photon Infrared Laser Pumping of
Polyatomic Molecules. By G.P. Quigley .............................. 134
Coherent Pulse Propagation Effects in Multilevel Molecular Systems.
By C.D. Cantrell, W.H. Louisell, and J.F. Lam ...................... 138
IX
The Influence of Intensity and Laser-Energy Fluence in Unimolecular
Reactions Induced by Monochromatic Infrared Radiation (URIMIR).
By M. Quack ........................................................ 142
On the Dynamics of Multiphoton Dissociation of Polyatomic
Molecules II. Application to 03. By K.D. Hansel .................... 145
Nonthermal Theory of Threshold Behaviour of Collisionless
Multiphoton Dissociation. By H. Friedmann .......................... 149
An Anharmonic Model for Molecular Photo-Excitation.
By P.G. Harper ..................................................... 152
Dynamic Stark Splitting of Multiphoton Absorption Resonances.
By P.L. Knight ..................................................... 155
Polarization Selection Rules for Two-Photon Processes.
By B.R. Marx and L. Allen 158
Doppler-Free Raman Spectroscopy and Suppression of Molecular
Doppler-Broadened Transitions Induced by Laser Field.
By A.K. Popov and L.N. Talashkevich ................................ 161
Laser-Controlled Unimolecular and Bimolecular Processes:
Field-Dependent Rate "Constants". By A.M.F. Lau .................... 163
Laser-Induced Predissociation of Diatomic and Polyatomic Molecules
by the Photo-Cata lyti c Effect. By A. M. F. Lau ....................... 167
Possibility of Hole Burning in Single Quantum Power Spectrum Due to
Autler-Townes Splitting. By J.V. Moloney and F.H.M. Faisal ......... 171
Computation of Rovibrational Multiphoton Spectra: Application to CO.
By J.V. Moloney and F.H.M. Faisal .................................. 173
Crossed Laser and Molecular Beam Study of Multiphoton Dissociation
of C2F5Cl. By D.J. Krajnovich, A. Giardini-Guidoni, Aa.S. Sudb~,
P.A. Schulz, Y.R. Shen, and Y.T. Lee ............................... 176
Study of Primary Characteristics of Multiple IR Photon Excitation
and Dissociation of CF3I. By V.N. Bagratashvili, V.S. Doljikov,
V.S. Letokhov, and E.A. Ryabov ..................................... 179
Photofragment Spectroscopy of Multiple Photon Dissociation by Laser
Induced Fluorescence. By R. Schmiedl, R. Bottner, H. Zacharias,
U. Meier, D. Feldmann, and K.H. Welge .............................. 186
x
Laser-Excited Fluorescence Studies of IR Multiple Photon Dissociation
Fragments: NH2(2B1) from CH3NH2 and NH3. By G. Hancock,
R.J. Hennessy, and T. Villis ....................................... 190
Time Behavior of CN Radicals in Laser-Initiated Thermal
Isomeriza.tion of CH3NC. By D.S. Bethune, J.R. Lankard, M.M.T. Loy,
J. Ors, and P.P. Sorokin ........................................... 193
Laser-Induced Decomposition of Methanol: A Comparative Study Using
Pulsed HF and CO2 Lasers. By R. Bhatnagar, P.E. Dyer,
and G.A. Oldershaw ................................................. 195
IR Laser Sensitised Chemical Reactions of Polyatomic Molecules.
By C. Steel, V. Starov, P. John, R.G. Harrison, and R. Leo ......... 198
Excitation of Ammonia in the Megawatt Region Using a CO2 Laser.
By V. Starov, C. Steel, S. Butcher, R.G. Harrison, P. John,
and R. Leo ......................................................... 201
Reaction Between CH3N02 and H2 Induced by CO2 Laser Pulses.
By M. Neve de Mevergni es and P. Fettwei s ........................... 205
Multiphoton Dissociation in Formaldehyde.
By G. Koren and U. P. Oppenhei m ..................................... 209
Multiphoton Vacuum UV Photodissociation of Simple Polyatomic
Molecules. By A.P. Baronavski, V.M. Donnelly, and J.R. McDonald .... 213
Mass Selective Two-Photon Ionization of a Polyatomic Molecule.
By U. Boesl, H.J. Neusser, and E.W. Schlag ......................... 219
Part IV. Laser Control of Chemical Reactions
Laser-Induced Chemical Processes: Reactions with Oriented Reagents.
By R.N. Zare ....................................................... 225
Laser-Induced Fluorescence Study of the Reactions of F Atoms with
CH3I, CF3I and IC1. By L. Stein, J. Wanner, H. Figger,
and H. Walther ..................................................... 232
A Laser-Induced Fluorescence Study of the Reaction
Ca + CC14-+ CaCl + CC13. By A. Schultz and W. Schmidt .............. 236
cw Laser-Induced Fluorescence Study of BA + S02: Vibronic Distribution
of BaO as a Function of Collisional Energy. By R. Dirscherl
and H.U. Lee ....................................................... 239
XI
