Published October 1991
| public
Journal Article
Global Potential Energy Contour Plots for Chemical Reactions. Muttiple Reaction Paths, Bifurcations, and Applicability of Transition-State Theory
- Creators
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Marcus, R. A.
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.
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.Additional details
- Eprint ID
- 58334
- Resolver ID
- CaltechAUTHORS:20150617-150657971
- NSF
- Created
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2015-06-19Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Noyes Laboratory of Chemical Physics
- Other Numbering System Identifier
- 8399