Imaging in Chemical Dynamics

415 Pages·2001·43.076 MB·English

by  Arthur G. Suits and Robert E. Continetti (Eds.)

Imaging in Chemical Dynamics
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In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
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In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
ACS SYMPOSIUM SERIES 770
Imaging in Chemical Dynamics
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American Chemical Society, Washington, DC
In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
Library of Congress Cataloging-in-PublicationD ata
Imaging in Chemical Dynamics / Arthur G. Suits, editor, Robert E. Continetti, editor.
p. cm.—(ACS symposium series ; 770)
Includes bibliographical references and index.
ISBN 0-8412-3690-9
org 01 1. Molecular dynamics—Congresses. 2. Imaging systems in Chemistry—Congresses.
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7, 10 for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48-1984.
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PRINTED IN THE UNITED STATES OF AMERICA
In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
Foreword
1 HE ACS SYMPOSIUM SERIES was first published in 1974 to provide a
mechanism for publishing symposia quickly in book form. The purpose
of the series is to publish timely, comprehensive books developed from
ACS sponsored symposia based on current scientific research.
Occasionally, books are developed from symposia sponsored by other
organizations when the topic is of keen interest to the chemistry
audience.
g Before agreeing to publish a book, the proposed table of contents is
cs.orw001 reviewed for appropriate and comprehensive coverage and for interest to
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7, 2102 As a rule, only original research papers and original review papers
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In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
Preface
Chemical dynamics is a field poised at the intersection between chemistry
and physics, relying on sophisticated experimental and theoretical techniques to
answer, in rich quantum mechanical detail, the most basic questions one can ask
about the dynamics of fundamental chemical reactions, questions such as: What
are the products in a given reaction or photochemical process? Which part of a
molecule is most reactive? What approach geometries are important? Where does
g the energy go in a reaction? How is the angular momentum distributed in the
s.or001 products?. The importance of questions such as these lies in their general nature
acpr and the deep understanding that the answers can provide. Practical chemical
s.0.
ub77 systems, from planetary atmospheres to automobile engines, all feature a vast array
p0
p://01- of elementary reactions involving large and complex molecules, and these systems
htt20 are far too numerous to be modeled in detailed from first principles. A predictive
012 | 1/bk- understanding of macroscopic chemical systems thus can only be built upon a
22 foundation of knowledge of the general trends and underlying principles governing
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6O ing new advances in the field in several key areas.
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wu applications of imaging techniques in chemical dynamics. As the presentations at
Do P the symposium and the 21 chapters in this volume indicate, imaging methods have
provided important insights into diverse phenomena in chemical reaction
dynamics. Although a large number of the experimental studies presented here are
based on CCD-camera ion-imaging methods, a number of contributions use event-
wise three-dimensional methods appropriate for coincidence measurements. A
driving force behind the organization of this symposium was a desire to bring the
scientists using these distinct approaches together for an exchange of ideas and
problems. In that regard, this symposium follows the 1993 "Workshop on Imaging
Methods" held at Neve Ilan, Israel, organized by George McBane and Daniel
Zajfman, and attended by some 44 researchers from around the world. This
symposium at the 212th ACS National Meeting in New Orleans, Louisiana, was the
next international meeting specifically intended to bring together researchers using
imaging methods for the study of chemical dynamics. The purpose of this volume
is to showcase these advances, provide a useful reference for those entering the
xi
In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
field, and foster new developments and new directions. We believe that the book
provides a timely snapshot of the development of this important tool in modern
chemical dynamics.
Acknowledgments
We thank Professor G. C. Schatz for the invitation to organize an ACS
Symposium on this topic, and the Petroleum Research Fund of the ACS for grant-
in-aid number 33793-SE in support of this symposium. We also thank Anne
Wilson and Kelly Dennis of the ACS Editorial Staff for their help in producing this
volume. Finally, we wish to thank all of the authors for their stimulating
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bs.70. ARTHUR G. SUITS
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In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
Chapter 1
Imaging in Chemical Dynamics: The State
of the Art
Arthur G. Suits1 and Robert E. Continetti2
1Chemical Sciences Division, Ernest Orlando Lawrence Berkeley
g National Laboratory, Berkeley, CA 94720
cs.orh001 2Department of Chemistry and Biochemistry, University of California
ac at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0314
http://pubs.2001-0770.
012 | 1/bk-
22
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d bon showcasing the broad range of applicability of these powerful
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Introduction
Chemical dynamics is a thriving enterprise, a field continually spurred to new
frontiers by technological advances. Molecular beams and lasers have each played
Permanent address: Department of Chemistry, State University of New York,
Stony Brook, New York, 11794, and Department of Chemistry, Brookhaven
National Laboratory, Upton NY, 11973
© 2001 American Chemical Society 1
In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
2
key roles in stimulating such advances at various times in the history of the field.
Beginning in the late 1980s, ion imaging emerged as a uniquely powerful combination
of these experimental tools. With the advent of the velocity map imaging method ten
years later, the applications of imaging to chemical dynamics experienced a renewed
explosion of interest, and much of this recent work is illustrated in this volume.
Although the use of ion imaging methods in chemical dynamics is often dated to
work by Chandler and Houston(i), application of position sensitive detection to
problems in physics has a long history, shown for example in the 1992 Nobel prize
awarded to Georges Charpak for the development of the multiwire proportional
counter. These techniques have typically been employed in an event-wise approach
that is not so well suited to the low repetition-rate nanosecond lasers that have been
g the workhorses of the chemical dynamics field. These methods are ideal, however, for
or01 application in quasi-continuous modes at accelerators and synchrotrons, with high-
acs.ch0 repetition rate lasers, and particularly for coincidence applications. The lines between
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22 provide a convenient means of separating the broader field into identifiable camps.
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d bon is generally considered to be the 1987 paper by David Chandler and Paul Houston on
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Do P coworkers(2,i), as early as 1967 used a coated reaction vessel to demonstrate that
photolysis of molecules by polarized lasers can give rise to anisotropic distributions of
products. Although this approach was clearly limited in scope, it provided a dramatic
mapping of the phenomenon under study. It is precisely this compelling "analog"
aspect of imaging that is both its power and its joy. Since 1987, the ion imaging
technique has been applied, with surprisingly little modification, to a vast number of
problems in chemistry and physics, and we will present many examples below. We
will not here attempt a review of the field of ion imaging or the recent introduction of
the higher-resolution VELMI technique; this has been accomplished in a number of
other recent reviews(4-#). Instead, we will highlight examples of current work, some
In Imaging in Chemical Dynamics; Suits, A., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.