Table Of ContentFast Reactions in Energetic Systems
NATO ADVANCED STUDY INSTITUTES SERIES
Proceedings of the Advanced Study Institute Programme, which aims
at the dissemination of advanced knowledge and
the formation of contacts among scientists from different countries
The series is published by an international board of publishers in conjunction
with NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical and D. Reidel Publishing Company
Physical Sciences Dordrecht, Boston and London
D Behavioural and Sijthoff & Noordhoff International
Social Sciences Publishers
E Applied Sciences Alphen aan den Rijn and Germantown
U.S.A.
Series C - Mathematical and Physical Sciences
Volume 71 - Fast Reactions in Energetic Systems
Fast Reactions
in Energetic Systems
Proceedings of the NATO Advanced Study Institute
held at Preveza, Greece, July 6 -19, 1980
edited by
CHRISTOS CAPELLOS
and
RA YMOND F. WALKER
Energetic Materials Division, Large Caliber Weapon Systems Laboratory,
U.S. Army Armament Research and Development Command,
Dover, New Jersey, U.SA.
D. Reidel Publishing Company
Dordrecht: Holland / Boston: U.S.A. / London: England
Published in cooperation with NATO Scientific Affairs Division
Library of Congress Cataloging in Publication Data
NATO Advanced Study Institute (1980: Preveza, Greece)
Fast reactions in energetic systems.
(NATO advanced study institute series. Series C: Mathematical and
physical sciences; v. 71)
Includes index.
1. Chemical reaction, Rate of- Congresses. I. Capellos, Christos.
II. Walker, Raymond F. III. Title. IV. Series.
QD502.N36 1980 541.3' 94 81-8528
AACR2
ISBN-13:978-94-009-8039-6 e-ISBN-13:978-94-009-85 I 1-7
DOl: 10.1007/978-94-009-8511-7
Published by D. Reidel Publishing Company
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Copyright © 1981 by D. Reidel Publishing Company, Dordrecht, Holland
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TABLE OF CONTENTS
PREFACE ix
ACKNOWLEDGMENTS x
OPENING ADDRESS 1
C. Capellos
CURRENT TRENDS IN RESEARCH AND
DEVELOPMENT IN THE U.S. 5
G. Gamota
TECHNOLOGY TRENDS AND RESEARCH
REQUIREMENTS INVOLVING FAST
ENERGETIC PROCESSES 23
R. F. Walker
FAST MOLECULAR PROCESSES AND SUGGESTED
RESEARCH DIRECTIONS FOR ENERGETIC
MATERIALS 33
C. Capellos
REACTION RATES INCLUDING FAST
REACTIONS IN ENERGETIC SYSTEMS 47
H. Eyring, M. S. Jhon, and
T. Ree
PICOSECOND REACTION KINETICS 55
P. M. Rentzepis
FAST REACTION STUDIES OF ORGANIC
IONS IN SOLUTION 95
L. M. Dorfman
SOME ASPECTS OF GAS PHASE ION
CHEMISTRY III
C. Lifshitz
ACTIVATION AND DEACTIVATION OF
VIBRATIONALLY HIGHLY EXCITED STATES 125
J. Troe
vi TABLE OF CONTENTS
SOME NEW APPLICATIONS OF KINETIC
SPECTROSCOPY IN SHOCK WAVES 141
J. Troe
FUNDAMENTAL ASPECTS OF FREE-RADICAL
REACTIVITY AND CHAIN REACTIONS 153
P. Gray
THERMAL EXPLOSION FUNDAMENTALS - UNIFICATION
OF THERMAL AND CHAIN-BRANCHING THEORIES OF
REACTION AND IGNITION - THERMOKINETIC
INTERPRETATION OF HYDROCARBON OXIDATION 171
P. Gray
COMBUSTION REACTION MECHANISMS FROM
IGNITION DELAY TIMES 193
A. Lifshitz
COHERENT ANTI-STOKES RAMAN SCATTERING 219
J. P. Taran
GAS DYNAMIC EFFECTS OF FAST EXOTHERMIC
REACTIONS 245
J. H. S. Lee and C. Guirao
FAST REACTIONS IN DISPERSED HETEROGENEOUS
ENERGETIC SYSTEMS 315
J. A. Nicholls
SOME FACTORS INFLUENCING THE
T~~NSITION
FROM DEFLAGRATION TO DETONATION 379
H. Eyring
ENERGETIC NITROAROMATIC TRANSIENTS AND
THEIR ROLE IN CONTROLLING THE
SENSITIVITY OF EXPLOSIVES 401
C. Capellos and S. Iyer
HIGH POWER PICOSECOND PHOTOLYSIS OF
SIMPLE ORGANIC MOLECULAR GASES 419
B. B. Craig, W. L. Faust,
L. S. Goldberg, J. M. Schnur,
P. E. Schoen, and R. G. Weiss
AN OBSERVATION OF COLLISION-FREE,
INTRAMOLECULAR VIBRATIONAL
REDISTRIBUTION IN SI p-FLUOROTOLUENE 433
D. A. Dolson, C. S. Parmenter, and
B. M. Stone
TABLE OF CONTENTS vii
VIBRATIONAL RELAXATION IN MOLECULAR
LIQUIDS .. 445
T. Dorfmuller and D. Samios
COUPLING OF MOLECULAR TO LATTICE
VIBRATIONAL MODES IN ENERGETIC
SOLIDS: RAMAN SPECTROSCOPIC STUDIES 461
z.
Iqbal and F. J. Owens
COHERENT ANTI-STOKES RAMAN
SPECTROSCOPY IN PROPELLANT
FLAMES 473
L. E. Harris and M. McIlwain
TEMPERATURE MEASUREMENTS OF SHOCKED
ENERGETIC MATERIALS BY TIME-RESOLVED
INFRARED RADIOMETRY 485
W. G. Von Holle
MEASUREMENT OF IGNITION KINETICS
IN LIQUIDS UNDER PRESSURE 503
C. M. Lownds and R. Hughes
DECREASING PROGRESSION OF THE
DECOMPOSITION RATE OF EXPLOSIVE
SUBSTANCES AT HIGH TEMPERATURES 515
J. J. Janswoude and H. J. Pasman
LASERPYROLYSIS OF HIGH ENERGETIC
MATERIALS 523
A. Pfeil, N. Eisenreich and
H. H. Weidlich
MODEL OF THE KINETICS OF HIGH
TEMPERATURE FREE RADICAL
REACTIONS 531
N. C. Peterson, T. Ishii,
and W. Braun
QUANTUM MECHANICAL TUNNELING IN
FREE RADICAL REACTIONS 541
V. Malatesta, K. U. Ingold, and
C. Chatgilialoglu
STUDIES ON SOME TRIFLUOROMETHYL
NITROXIDE RADICALS BY EPR
SPECTROSCOPY 553
C. Chatgilialoglu, K. U. Ingold,
and v. Malatesta
viii TABLE OF CONTENTS
EXPERIMENTAL ION-MOLECULE DYNAMICS
INCLUDING REACTIONS INVOLVING
EXCITED STATES 561
W. S. Koski
RELIABLE AB INITIO QUANTUM CHEMICAL
CALCULATIONS FOR ENERGETIC SPECIES 569
J. J. Kaufman
THE STUDY OF FAST SHOCK-INDUCED
DISSOCIATION BY COMPUTER
MOLECULAR DYNAMICS 611
A. M. Karo, and J. R. Hardy
STUDIES OF FAST REACTIONS IN
DETONATIONS 645
C. L. Mader
RESONANCE FLUORESCENCE OF ATOMS
AT HIGH PHOTON DENSITIES 659
C. Mavroyannis
HIGH DENSITY EXCITATION CALCULATIONS
IN MOLECULAR SOLIDS: A MONTE CARLO
STUDY 685
P. Argyrakis, J. Hoshen, and
R. Kopelman
A REACTION MECHANISM IN THE SHOCK
INITIATION OF DETONATION. A THEORETICAL
STUDY 695
J. Alster, N. Slagg, M. J. S Dewar,
J. P. Ritchie, and C. Wells
INFORMAL DISCUSSION 711
LIST OF PARTICIPANTS
743
KEY WORDS 751
PREFACE
This book presents the formal lectures and contributed papers
given at the NATO Advanced Study Institute on Fast Reactions in
Energetic Systems, which took place in Preveza, Greece, during the
period 6-19 July 1980.
The material describes experimental observations and the more
advanced theoretical aspects of certain types of fast reactions
and energy or charge transfer processes which are usually complete
in periods of 10-6 - 10-12 seconds. Furthermore, it discusses the
role of macroscopic and molecular processes in the ignition,
combustion, deflagration, and detonation of solid, liquid, and
gaseous chemical systems.
Various papers deal with the ability of molecules to absorb
and transmit the different forms of energy provided by shock,
light, thermal, or electron pulses, and to contribute to the
propagation of reactions under high temperatures and pressures.
The role of energy pumped or transferred to electronic or
vibrational states is discussed in terms of excitation,
ionization, bond scission, and the formation of free radicals.
The dynamics and reactivity of ionic species, electronically and
vibrationally excited states, and free radicals are described for
various gaseous, liquid, and solid systems.
The proceedings include presentations of theoretical and
experimental techniques to describe and observe the phenomena.
Selected theoretical papers deal with topics such as the classical
thermodynamic - fluid dynamic descriptions of initiation, defla
gration, and detonation; computer molecular dynamics; and
ab-initio and semi-empirical quantum chemical calculations of the
structure and stability of typical molecules, their reaction prod
ucts and intermediates. Powerful diagnostic tools are presented,
such as nanosecond and picosecond pulsed radiolysis, and laser
kinetic spectroscopy, coherent anti-Stokes Raman spectroscopy, and
shock tube kinetic spectroscopy, which have contributed a great
deal to the study of fast reactions.
The purpose of the proceedings is to provide the reader with
a rather broad perspective on the various types of fast reactions
and energy transfer processes, and self-sustained fast reactions
in energetic materials. It is intended to indicate the prospects
and needs for future research in energetic materials, and to make
it apparent that collaborative research should be initiated to
shed light into areas of importance. Of critical importance is
IX
x PREFACE AND ACKNOWLEDGMENTS
the elucidation of the exothermic molecular processes and other
crucial parameters which control the energy release in ignition,
combustion, and the propagation of reactions that lead to
deflagration and detonation in chemical systems.
The proceedings should be of interest to graduate and post
graduate students who are taking courses or starting research in
the relevant scientific areas, and to all scientists who have an
interest in the topics described. Necessary introductory informa
tion is provided on fast reactions, before continuing to more
advanced concepts and newer theoretical and experimental tech
niques. Much of the information in the proceedings has not quite
reached the textbooks on fast reactions and the theory of
explosives.
CHRISTOS CAPELLOS
RAYMOND F. WALKER
ACKNOWLEDGMENTS
We should like to express our gratitude to the members of the
Organizing Committee, Professor M.I. Karayannis, Dr. H. Schubert,
and Professor B.A. Thrush, F .R. S., for their encouraging
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.
Mrs. G. McDougal and Mrs. J. C. Nelson provided invaluable
secretarial assistance in planning the meeting, and Ms. N.
Papastergiou provided efficient secretarial support and did much
to create a very congenial atmosphere during the meeting.
Mrs. S. Van Ry, Ms. C. Novak, and Mrs. G. McDougal were
extremely diligent and efficient over an extended period in
providing the typing and editorial assistance that was necessary
for the completion of this book in good time. The editors and
participants in the Institute are deeply indebted to all these
individuals for their unfailing reliability, enthusiastic support,
and generous concern. We hope that to some degree the success of
the meeting and the publication of the proceedings will be its own
reward.
Last but not least, we should like to express our gratitude
to the NATO Scientific Affairs Division, National Science
Foundation, Office of Naval Research, Air Force Office of
Scientific Research, U.S. Army Research Group (ARO) and the
Energetic Materials Division (LCWSL-ARRADCOM) for providing
financial support for the meeting.
