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Perspective on “The transition state method”

Wigner E (1938) Trans Faraday Soc 34: 29–41

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Book cover Theoretical Chemistry Accounts

Abstract

A perspective is provided on Wigner’s classic paper on transition-state theory (TST). After providing a brief review of the historical context of this work, we review its key contributions including Wigner’s dynamical perspective on TST, the fundamental assumption of TST, and the upper-bound property of classical TST. A discussion is also presented of subsequent progress in the field, which was stimulated by this work. This progress includes the following:

  1. 1.

    Demonstrations of the validity of the fundamental assumption for classical systems.

  2. 2.

    Further investigations into the classical foundations of TST that helped elucidate relationships between classical trajectories and TST.

  3. 3.

    The development of a variational form of the theory.

  4. 4.

    The development of variational TST into a quantitative tool for predicting rate constants.

  5. 5.

    The search for an “exact” quantum mechanical version of TST.

  6. 6.

    The development of TST-like expressions for the exact quantum mechanical rate constant.

  7. 7.

    The extension of TST to reactions in condensed phases.

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Author information

Authors and Affiliations

  1. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, 93352, USA

    Bruce C. Garrett

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  1. Bruce C. Garrett
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Editor information

Editors and Affiliations

  1. Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, 55455-0431, Minneapolis, MN, USA

    Christopher J. Cramer  & Donald G. Truhlar  & 

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© 2000 Springer-Verlag Berlin Heidelberg

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Garrett, B.C. (2000). Perspective on “The transition state method”. In: Cramer, C.J., Truhlar, D.G. (eds) Theoretical Chemistry Accounts. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-10421-7_10

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  • DOI: https://doi.org/10.1007/978-3-662-10421-7_10

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-67867-0

  • Online ISBN: 978-3-662-10421-7

  • eBook Packages: Springer Book Archive

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