Advances in Chemical Reaction Dynamics

607 Pages·1986·26.724 MB·English

by  R. Bersohn (auth.), Peter M. Rentzepis, Christos Capellos (eds.)

Advances in Chemical Reaction Dynamics
NATO ASI Series
Advanced Science Institutes Series
A series presenting the results of activities sponsored by the NATO 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 D. Reidel Publishing Company
and Physical Sciences Dordrecht, Boston, Lancaster and Tokyo
D Behavioural and Social Sciences Martinus Nijhoff Publishers
E Engineering and The Hague, Boston and Lancaster
Materials Sciences
F Computer and Systems Sciences Springer-Verlag
G Ecological Sciences Berlin, Heidelberg, New York and Tokyo
Series C: Mathematical and Physical Sciences Vol. 184
Advances in
Chemical Reaction Dynamics
edited by
Peter M. Rentzepis
University of California, Department of Chemistry,
Irvine, California, U.S.A.
and
Christos Capell os
Energetics and Warheads Division,
Armament Engineering Directorate,
US Army Armament Research, Development and Engineering Center,
Dover, New Jersey, U.S.A.
D. Reidel Publishing Company
Dordrecht / Boston / Lancaster / Tokyo
Published in cooperation with NATO Scientific Affairs Division
Proceedings of the NATO Advanced Study Institute on
Advances in Chemical Reaction Dynamics
Iraklion, Crete, Greece
25 August-7 September 1985
Library of Congress Cataloging in Publication Data
NATO Advanced Study Institute on Advances in Chemical Reaction Dynamics (1985 , Crete)
Advances-in chemical reaction dynamics.
(NATO ASI series. Series C, Mathematical and physical sciences; vol. 184)
"Proceedings of the NATO Advanced Study Institute on Advances in Chemical Reaction
Dynamics,lraklion, Crete, Greece, 25 August-7 September, 1985"
"Published in cooperation with NATO Scientific Affairs Division."
Includes index.
1. Chemical reaction, Rate of- Congresses. 2. Chemical reaction, Conditions and
LawS-Congresses. I. Rentzepis, Peter M., 1934- . II. Capellos, Christos. III. Title.
IV. Series: NATO ASI series. Series C, Mathematical and physical sciences; vol. 184.
QD502.N365 1985 541.3'94 8~17441
ISBN-13: 978-94-0 I 0-8604-2 e-ISBN -13: 978-94-009-4734-4
DOT: 10.1007/978-94-009-4734-4
Published by D. Reidel Publishing Company
P.O. Box 17, 3300 AA Dordrecht, Ho"and
Sold and distributed in the U.S.A. and Canada
by Kluwer Academic Publishers,
101 Philip Drive, Assinippi Park, Norwe", MA 02061, U.S.A.
In a" other countries, sold and distributed
by Kluwer Academic Publishers Group,
P.O. Box 322, 3300 ,A,H Dordrecht, Ho"and
D. Reidel Publishing Company is a member of the Kluwer Academic Publishers Group
A" Rights Reserved
© 1986 by D. Reidel Publishing Company, Dordrecht, Ho"and.
Softcover reprint of the hardcover 1st edition 1986
No part of the material protected by this copyright notice may be reproduced or utilized
in any form or by any means, electronic or mechanical, including photocopying, recording
or by any information storage and retrieval system, without written permission from the
copyright owner.
TABLE OF CONTENTS
PREFACE ix
ACKNOWLEDGMENTS x
TRANSLATIONAL ENERGY RELEASE IN THE
PHOTODISSOCIATION OF AROMATIC MOLECULES
R. Bersohn
THE STRUCTURE OF THE TRANSITION STATE 21
AS INFERRED FROM PRODUCT STATE DISTRIBUTIONS
R. Bersohn
STUDIES OF RAPID INTRAMOLECULAR AND 41
INTRAIONIC DYNAMIC PROCESSES WITH
TWO-COLOR PICOSECOND LASERS AND MASS
SPECTROMETRY
D.A. Gobeli, J.S. Simon,
D.M. Szaflarski, and
M.A. EI-Sayed
DETECTION OF DIPOLAR CONTRIBUTION TO THE 57
MECHANISM OF THE TRIPLET-TRIPLET ENERGY
TRANSFER PROCESS IN MOLECULAR SOLIDS
J.R. Morgan, H.S. Niederwald,
and M.A. EI-Sayed
GAS PHASE CHAIN POLYMERIZATION 71
H. Reiss
COMMENTS ON CLUSTERS IN BEAMS, SPECTROSCOPY, 115
AND PHASE TRANSITIONS
H. Reiss
ENERGY TRANSFER IN COLLISIONS OF POSITIVE 135
HALOGEN IONS WITH RARE GAS ATOMS
M. Hotokka, B. Roos,
K. Balasubramanian,
R.B. Sharma, N.M. Semo,
and W.S. Koski
vi TABLE OF CONTENTS
CORRELATIONS IN PICOSECOND PULSE SCATTERING: 145
APPLICATIONS FOR FAST REACTION DYNAMICS
B. Van Wonterghem and A. Persoons
PICOSECOND TRANSIENT RAMAN STUDIES: 151
TECHNIQUE AND APPLICATIONS
J.B. Hopkins and P.M. Rentzepis
PICOSECOND SPECTROSCOPY OF IRON PORPHYRINS 165
AND HEMOPROTEINS
K.D. Straub and P.M. Rentzepis
INTERMOLECULAR PROTON TRANSFER 171
D. Huppert and E. Pines
MOLECULAR DYNAMICS OF LIQUID PHASE REACTIONS 179
BY TIME-RESOLVED RESONANCE RAMAN SPECTROSCOPY
G.H. Atkinson
HIGH SENSITIVITY, TIME-RESOLVED ABSORPTION 207
SPECTROSCOPY BY INTRACAVITY LASER TECHNIQUES
G.H. Atkinson
DYNAMICS OF EXCITED STATES OF AN ATOM 229
INTERACTING WITH STRONG LASER FIELDS
C. Mavroyannis
DYNAMICS OF EXCITED STATES OF TWO IDENTICAL 251
ATOMS INTERACTING WITH STRONG LASER FIELDS
C. Mavroyannis
STIMULATED ONE-PHOTON AND MULTIPHOTON 267
PROCESSES IN STRONGLY DRIVEN MULTILEVEL
ATOMIC SYSTEMS
C. Mavroyannis
AB-INITIO MULTIREFERENCE DETERMINANT 289
CONFIGURATION INTERACTION (MRD-CI) AND
CASSCF CALCULATIONS ON ENERGETIC COMPOUNDS
J.J. Kaufman, P.C. Hariharan,
s. Roszak, C. Chabalowski,
M. van Hemert, M. Hotokka, and
R.J. Buenker
CRYSTAL STRUCTURES OF ENERGETIC COMPOUNDS: 311
AB-INITIO POTENTIAL FUNCTIONS AND AB-INITIO
CRYSTAL ORBITALS
J.J. Kaufman, P.C. Hariharan,
S. Roszak, J.M. Blaisdell, and
A.H. Lowrey
TABLE OF CONTENTS vii
THEORETICAL STUDIES OF THE C4 MOLECULE 327
J.P. Ritchie, H.F. King, and
W.S. Young
FRACTAL ASPECTS OF HETEROGENEOUS 339
CHEMICAL REACTIONS
P. Argyrakis and R. Kopelman
THE PROPAGATION OF TURBULENT FLAMES 345
AND DETONATIONS IN TUBES
J.H.S. Lee
KrF LASER INDUCED DECOMPOSITION OF 379
TETRANITROMETHANE
C. Capellos, S. Iyer,
Y. Liang, and L.A. Gamss
INFRARED LASER MULTIPHOTON DECOMPOSITION 395
OF 1,3,5-TRINITROHEXAHYDRO-S-TRIAZINE (RDX)
C. Capellos, S. Lee, S. Bulusu,
and L.A. Gamss
TRANSIENT PHOTOCHEMISTRY OF NITROBENZENE 405
AND NITRONAPHTHALENES
S. Iyer and C. Capellos
DYNAMICS OF THE COLLISION FREE UNIMOLECULAR 415
FRAGMENTATION OF PRIMARY ALKYL EPOXIDES
T.E. Adams, M.B. Knickelbein,
D.A. Webb, and E.R. Grant
COHERENT AND SPONTANEOUS RAMAN SPECTROSCOPY 425
IN SHOCKED AND UNSHOCKED LIQUIDS
S.C. Schmidt, D.S. Moore, D. Schiferl,
M. Chatelet, T.P. Turner, J.W. Shaner,
D.L. Shampine, and W.T. Holt
REACTION PRODUCTS OF ENERGETIC MATERIALS 455
HEATED BY SHORT LASER PULSES
H. Krause and A. pfeil
SPECTROSCOPY AS A TOOL TO PROBE LASER 459
INITIATION OF PRIMARY EXPLOSIVES
M.W. Leeuw, A.J.Th Rooijers,
and A.C. van der Steen
DISLOCATION PILE-UP MECHANISM FOR 469
INITIATION OF ENERGETIC CRYSTALS
R.W. Armstrong, C.S. Coffey,
and W.L. Elban
viiI TABLE OF CONTENTS
LASER EMISSION AT 502nm INDUCED BY 475
KrF LASER MULTIPHOTON DISSOCIATION
OF HgBr2
P. Papagiannakopoulos and
D. Zevgolis
THE DYNAMICS OF ELECTRIC FIELD EFFECTS 483
IN LOW POLAR SOLUTIONS: THE FIELD
MODULATION METHOD
A. Persoons and L. Hellemans
HIGH ELECTRIC FIELD PERTURBATION AND 503
RELAXATION OF DIPOLE EQUILIBRIA. A
HAZARDOUS UNDERTAKING?
L. Hellemans and A. Persoons
THE MECHANISM OF ENERGY STORAGE IN THE 525
REACTION CENTER IN PHOTOSYNTHETIC
BACTERIA AND ATTEMPTS TO SIMULATE PROCESSES
USING MONOLAYER ASSEMBLY TECHNIQUE
H. Kuhn
STRUCTURE AND DYNAMICS OF METAL-NUCLEIC 551
ACID INTERACTIONS
T. Theophanides and H.A. Tajmir-Riahi
DETECTION AND CHARACTERIZATION OF SHORT-LIVED 565
SPECIES BY NANOSECOND TIME-RESOLVED
SPECTROSCOPIC TECHNIQUES
J. Aubard, J.J. Meyer, R. Dubest,
A. Adenier, and P. Levoir
FORMATION, DECAY, AND SPECTRAL CHARACTERIZATION 571
OF SOME SULFONYL RADICALS
C. Chatgilialoglu
DENSITY AND CONCENTRATION FLU~TUATIONS IN 581
MACROMOLECULAR SYSTEMS AS PROBED BY DYNAMIC
LASER LIGHT SCATTERING
G. Fytas
LIST OF PARTICIPANTS 589
INDEX 599
PREFACE
This book contains the formal lectures and contributed papers
presented at the NATO Advanced Study Institute on. the Advances in
Chemical Reaction Dynamics. The meeting convened at the city of
Iraklion, Crete, Greece on 25 August 1985 and continued to
7 September 1985.
The material presented describes the fundamental and recent
advances in experimental and theoretical aspects of, reaction
dynamics. A large section is devoted to electronically excited
states, ionic species, and free radicals, relevant to chemical sys
tems. In addition recent advances in gas phase polymerization,
formation of clusters, and energy release processes in energetic
materials were presented. Selected papers deal with topics such as
the dynamics of electric field effects in low polar solutions, high
electric field perturbations and relaxation of dipole equilibria,
correlation in picosecond/laser pulse scattering, and applications to
fast reaction dynamics. Picosecond transient Raman spectroscopy
which has been used for the elucidation of reaction dynamics and
structural changes occurring during the course of ultrafast chemical
reactions; propagation of turbulent flames and detonations in gaseous·
energetic systems are also discussed in some detail. In addition a
large portion of the program was devoted to current experimental and
theoretical studies of the structure of the transition state as
inferred from product state distributions; translational energy
release in the photodissociation of aromatic molecules; intramolecu
lar and intraionic dynamic processes. Dipolar contribution to the
mechanism of triplet-triplet energy transfer in molecular solids;
dynamics of excited states of atoms interacting with strong laser
fields, as well as other important topics.
The purpose of the proceedings is to provide the reader with a
rather broad perspective on the current theoretical aspects and
recent experimental observations in the field of reaction dynamics.
Furthermore, the material presented in the proceedings should make
apparent the future trends for research and demonstrate the signif
icance of collaborative research between theorists and experimen
talist in areas of importance to the understanding of chemical reac
tion dynamics specially of large organic, energetic, and biological
molecules.
The proceedings should be of interest to graduate and post
graduate students who are involved or starting research in these
scientific areas, and to scientists who are actively pursuing
research in reaction kinetics. Appropriate introductory overviews
are provided in this text on the various aspects of reaction
ix
x PREFACE AND ACKNOWLEDGMENTS
dynamics, which might be of help before continuing to more advanced
concepts and the recent theoretical and experimental papers pre
sented. An appreciable part of the information contained in the
proceedings has not appeared yet in the textbooks on chemical reac
tion dynamics.
P.M. RENTZEPIS
C. CAPELLOS
ACKNOWLEDGMENTS
We express our appreciation to Professor P. Papagianakopoulos
for his reliable assistance in organizing the NATO Advanced Study
Institute. Special thanks are due to all lecturers and authors for
their cooperation in preparing their manuscripts, excellent delivery
of lectures, and dedication to the meeting.
Miss Irene Fedum provided invaluable secretarial assistance in
preparation for the meeting, and Ms. Carol Novak for the expert typ
ing of manuscripts.
Last, but not least, we should like to express our gratitude to
the NATO Scientific Affairs Division, US Army Research Group (ERO)
and the Energetic Materials Division (LCWSL-ARDC) for granting finan
cial support for the meeting.