Application of variational transition-state theory and the unified statistical model to H + Cl2 → HCl + Cl

Bruce C. Garrett, Donald G Truhlar, Roger S. Grev

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

Microcanonical variational theory with a semiclassical adiabatic ground-state transmission coefficient predicts the thermal rate constant for collinear H + Cl2 within 6% for 200-1000 K and the kinetic isotope effect kH/kD within 6 or 9% (depending on the detailed assumptions in the transmission coefficient) over the same temperature range. Other versions of variational transition-state theory and even conventional transition-state theory with semiclassical or quantum mechanical adiabatic ground-state transmission coefficients are also tested and show similar accuracy. The variational calculations predict a greater breakdown of conventional transition-state theory at higher temperatures and for three-dimensional reactions. The unified statistical theory is less accurate than variational transition-state theory for the magnitudes of the collinear rate constants, but more accurate for collinear kinetic isotope effects.

Original languageEnglish (US)
Pages (from-to)1749-1752
Number of pages4
JournalJournal of physical chemistry
Volume84
Issue number13
StatePublished - Dec 1 1980

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