Generalized transition state theory and least-action tunneling calculations for the reaction rates of H(D) + H/sub 2/(n=1). -->. H/sub 2/(HD) + H

Journal Article · Thu May 23 04:00:00 EDT 1985 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100257a014· OSTI ID:5133777

Garrett, B C; Truhlar, D G

Improved canonical variational theory calculations are reported with least-action transmission coefficients for the reactions H + H/sub 2/(n=1) and D + H/sub 2/(n=1), where n denotes the vibrational quantum number, in both collinear and three-dimensional worlds and for three different potential surfaces. Where possible comparisons to accurate or more complete quantal calculations are made and very good agreement is found. For the three-dimensional reaction and the most accurate available potential energy surfaces comparisons to all available experimental determinations at 297-356 K are made; the experimental results are larger than the calculated rate constants by factors of (in chronological order) 26, 17, 60, 5, and 8. The disagreement is probably due in large part to the difficulty of experiments. 50 references, 1 figures, 7 tables.

• Research Organization: Chemical Dynamics Corp., Columbus, OH
• DOE Contract Number: AC02-79ER10425
• OSTI ID: 5133777
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:11; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMPLITUDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DEUTERIUM
ELEMENTS
HYDROGEN
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
POTENTIALS
REACTION KINETICS
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
THEORETICAL DATA
TRANSITION AMPLITUDES
TUNNEL EFFECT
VARIATIONAL METHODS