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Determination of the Bottleneck Regions of Potential Energy Surfaces for Atom Transfer Reactions by Variational Transition State Theory

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Potential Energy Surfaces and Dynamics Calculations

Abstract

A major difficulty in the calculation of reliable equilibrium rate constants for gas-phase bimolecular reactions is the lack of accurate information about potential energy surfaces. The calculation of accurate, detailed dynamical quantities such as inelastic and reactive cross sections requires a knowledge of the potential energy surface over large regions of the configuration space. Thermal rate constants represent an average of such detailed dynamical quantities, and as a result they are less sensitive to fine features of the surface. Thus accurate thermal rate constants may be calculated using less information about the potential surfaces than is required to calculate more detailed quantities; one of the goals of the present chapter is to discuss which regions of the surfaces are most important in controlling the rates of chemical reactions.

Lando Research Fellow, 1979, 1980

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Author notes

  1. Bruce C. Garrett

    Present address: Chemical Dynamics Corporation, 1550 West Henderson Road, Suite N140, Columbus, OH, 43220, USA

  2. Roger S. Grev (Lando Research Fellow)

    Present address: University of Minnesota, Morris, MN, 56267, USA

Authors and Affiliations

  1. Department of Chemistry, University of Minnesota, Minneapolis, MN, 55455, USA

    Bruce C. Garrett, Donald G. Truhlar & Roger S. Grev (Lando Research Fellow)

  2. Battelle Columbus Laboratories, 505 King Avenue, Columbus, OH, 43201, USA

    Bruce C. Garrett

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Editors and Affiliations

  1. University of Minnesota, Minneapolis, Minnesota, USA

    Donald G. Truhlar

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Garrett, B.C., Truhlar, D.G., Grev, R.S. (1981). Determination of the Bottleneck Regions of Potential Energy Surfaces for Atom Transfer Reactions by Variational Transition State Theory. In: Truhlar, D.G. (eds) Potential Energy Surfaces and Dynamics Calculations. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-1735-8_24

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