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Global Potential Energy Contour Plots for Chemical Reactions. Muttiple Reaction Paths, Bifurcations, and Applicability of Transition-State Theory

Marcus, R. A. (1991) Global Potential Energy Contour Plots for Chemical Reactions. Muttiple Reaction Paths, Bifurcations, and Applicability of Transition-State Theory. Journal of Physical Chemistry, 95 (21). pp. 8236-8243. ISSN 0022-3654 . https://resolver.caltech.edu/CaltechAUTHORS:20150617-150657971

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Abstract

A global reduced-dimensional potential energy contour plot is described for the simultaneous representation of reactions X-3Y ⇌ X_2 + XY, X_3Y ⇌ X + X_2Y, and X_2 + YX ⇌ X_2Y + X, where the X's may be different. The analysis provides some insight into the nature of the transition states, the role of bifurcations, and the applicability of transition-state theory (TST). Recent results of a quantum chemistry calculation for the X = H, Y = 0 system are discussed in these terms. More generally, some Topographical conditions for the inapplicability of TST are suggested. This limitation of TST arises from a preempting of the transition state for one reaction by another and appears to be relatively rare.


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http://dx.doi.org/10.1021/j100174a042DOIArticle
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Additional Information:© 1991 American Chemical Society. Received: February 27, 1991; In Final Form: April 19, 1991. This research was supported by a grant from the National Science Foundation, and I am pleased to acknowledge its support. It is with a profound sadness that I dedicate this paper in this memorial issue to my colleague and friend for more than 30 years, Dick Bernstein. He stood and stands for all that is good in this scientific life-integrity, incisive thinking, vision, and a youthful joyousness in scientific inquiry. We all recognize that life has a natural limit, but it is when Nature takes a shortcut, as it did in Dick's case, that our sense of loss for all of us is the more acute.
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Caltech Noyes Laboratory of Chemical Physics8399
Issue or Number:21
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Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150617-150657971
Official Citation:Global potential energy contour plots for chemical reactions: multiple reaction paths, bifurcations, and applicability of transition-state theory R. A. Marcus The Journal of Physical Chemistry 1991 95 (21), 8236-8243 DOI: 10.1021/j100174a042
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58334
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 Jun 2015 01:17
Last Modified:03 Oct 2019 08:34

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