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Published October 1990 | Published
Journal Article Open

Ultrafast molecular reaction dynamics in real-time: progress over a decade


One of the goals of researchers in the field of reaction dynamics is to develop an understanding of the elementary steps involved in a chemical reaction on a molecular level (see e.g. Ref. 1). The century-old Arrhenius rate law, a phenomenological description of the temperature dependence of rates of reactions in bulk, has been used extensively to deduce activation energies and frequency factors. The activated complex theory (also referred to as absolute rate theory or transition-state theory, see e.g. Refs. 2, 3) postulated more than 50 years ago, provides a useful interpretation of the Arrhenius rate parameters in terms of molecular properties. These parameters contain practical information about rates, but they do not express the molecular details of a reaction. At this juncture, two types of questions can be raised--one concerning the effects of the environment on rates in condensed media, and the other, the purely molecular aspects of reactions in the absence of an environment, i.e. in an isolated molecular system. We restrict our attention to the latter case for the purposes of this review.

Additional Information

"Reprinted, with permission, from the Annual Review of Physical Chemistry, Volume 41 copyright 1990 by Annual Reviews, www.annualreviews.org" Over the last ten years, this research was supported primarily by the National Science Foundation and the Air Force Office of Scientific Research, hereby gratefully acknowledged. The efforts and dedication of a great number of graduate students and post-doctoral fellows, acknowledged in this review, have made this research possible. A.H.Z. wishes to thank R. A. Marcus, R. B. Bernstein, and R. Bersohn for many stimulating discussions; the fruits of some collaborations are acknowledged in the text. We are grateful to all our colleagues who provided us with preprints and reprints of their work. We hope that we were successful in including all relevant contributions and apologize to those whose work we did not have a chance to discuss. L.R.K. would like to thank the National Research Council for support through a postdoctoral Resident Research Associateship at the Jet Propulsion Laboratory, Caltech, administered by the NASA.

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