Title: improved canonical variational transition-state theory
Long Title: IUPAC Gold Book - improved canonical variational transition-state theory
DOI: 10.1351/goldbook.I02993
Status: current

Definition
A modification of canonical variational transition-state theory in which, for energies below the threshold energy, the position of the dividing surface is taken to be that of the microcanonical threshold energy. This forces the contributions to rate constant to be zero below the threshold energy. A compromise dividing surface is then chosen so as to minimize the contributions to the rate constant made by reactants having higher energies.

Related Terms
- canonical variational transition-state theory: https://goldbook.iupac.org/terms/view/C00790
- dividing surface: https://goldbook.iupac.org/terms/view/D01823
- rate constant: https://goldbook.iupac.org/terms/view/O04322
- threshold energy: https://goldbook.iupac.org/terms/view/T06366

Source
- PAC, 1996, 68, 149. 'A glossary of terms used in chemical kinetics, including reaction dynamics (IUPAC Recommendations 1996)' on page 168 (https://doi.org/10.1351/pac199668010149)

Other Outputs
- html: https://goldbook.iupac.org/terms/view/I02993/html
- json: https://goldbook.iupac.org/terms/view/I02993/json
- xml: https://goldbook.iupac.org/terms/view/I02993/xml

Citation: Citation: 'improved canonical variational transition-state theory' in IUPAC Compendium of Chemical Terminology, 5th ed. International Union of Pure and Applied Chemistry; 2025. Online version 5.0.0, 2025. 10.1351/goldbook.I02993
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Accessed: 2026-08-09T14:25:31+00:00