Application of variational transition-state theory and the unified statistical model to H + Cl/sub 2/. -->. HCl + Cl

Journal Article · Tue Jan 01 04:00:00 EST 1980 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100450a014· OSTI ID:6388978

Garrett, B C; Truhlar, D G; Grev, R S

Microcanonical variational theory with a semiclassical adiabatic ground-state transmission coefficient predicts the thermal rate constant for collinear H + Cl/sub 2/ within 6% for 200 to 1000 K and the kinetic isotope effect k/sub H/k/sub D/ 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. 5 tables.

• Research Organization: Univ. of Minnesota, Minneapolis
• DOE Contract Number: AC02-79ER10425
• OSTI ID: 6388978
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 84; 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
CHEMICAL REACTION KINETICS
CHLORINE
DEUTERIUM
ELEMENTS
ENERGY LEVELS
GROUND STATES
HALOGENS
HIGH TEMPERATURE
HYDROCHLORIC ACID
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INORGANIC ACIDS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MATHEMATICAL MODELS
MEDIUM TEMPERATURE
NONMETALS
NUCLEI
ODD-ODD NUCLEI
REACTION KINETICS
STABLE ISOTOPES
STATISTICAL MODELS
USES
VARIATIONAL METHODS