A new expression for the direct quantum mechanical evaluation of the thermal rate constant.

Journal Article · Sat May 15 04:00:00 EDT 2004 · J. Chem. Phys.

DOI:https://doi.org/10.1063/1.1697392· OSTI ID:961504

Medvedev, D M; Gray, S K

Based on the formalism of Miller, Schwartz, and Tromp [J. Chem. Phys. 79, 4889(1983)], we derive a new expression for the thermal rate constant for a chemical reaction. The expression involves an unperturbed, i.e., reactant or product channel Boltzmann operator for the imaginary time propagation, making it possible to compute efficiently the rate constant for a range of temperatures. We illustrate numerical aspects with an extensive study of the one-dimensional Eckart barrier problem, as well as a study of the three-dimensional (J = 0) D+H{sub 2} problem.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: SC
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 961504
• Report Number(s): ANL/CHM/JA-48478
• Journal Information: J. Chem. Phys., Journal Name: J. Chem. Phys. Journal Issue: 19 ; May 15, 2004 Vol. 120; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
BOLTZMANN EQUATION
CHEMICAL REACTIONS
DEUTERIUM
EVALUATION
RANGE
REACTION KINETICS
TEMPERATURE RANGE