Improved treatment of threshold contributions in variational transition-state theory

Journal Article · Thu Jun 26 04:00:00 EDT 1980 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100450a013· OSTI ID:6951873

Garrett, B C; Truhlar, D G; Grev, R S; Magnuson, A W

The improved canonical variational theory, presented previously for reaction rates in a classical mechanical world, has been extended to reactions in a quantum mechanical world where internal energies of reactants are quantized. A detailed discussion of vibrationally adiabatic models for transmission coefficients for conventional transition-state theory and three versions of variational transition-state theory are also presented. The relationship of the improved canonical variational transition-state theory to the classical limit of these transmission coefficients has been shown. The improved canonical variational theory and the new quantal and classical transmission coefficients are illustrated and tested by applications to quantal collinear and three-dimensional reactions rates for several reactions. Semiclassical approximations to the quantal transmission coefficients are also examined. Applications considered are collinear H + H/sub 2/ and isotopic analogs, Cl + H/sub 2/ and isotopic analogs, and I + H/sub 2/ and three-dimensional D + H/sub 2/, Cl + HD, I + H/sub 2/, I + D/sub 2/, O + H/sub 2/, and F + H/sub 2/.

• Research Organization: Univ. of Minnesota, Minneapolis
• DOE Contract Number: AC02-79ER10425
• OSTI ID: 6951873
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 84:13; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ATOMS
CHEMICAL REACTIONS
CHLORINE
DEUTERIUM
ELEMENTS
FLUORINE
HALOGENS
HYDROGEN
HYDROGEN ISOTOPES
IODINE
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NONMETALS
NUCLEI
ODD-ODD NUCLEI
OXYGEN
REACTION KINETICS
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