Thermal rate constant calculation using flux{endash}flux autocorrelation functions: Application to Cl+H{sub 2}{r_arrow}HCl+H reaction

Journal Article · Sat Nov 01 04:00:00 EST 1997 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.474959· OSTI ID:553986

Wang, H; Thompson, W H; Miller, W H ^[1]

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1. Department of Chemistry, University of , California (United States)

An efficient method was recently introduced by Thompson and Miller [J. Chem. Phys. {bold 106}, 142 (1997)] for calculating thermal rate constants using the flux{endash}flux autocorrelation function with absorbing boundary conditions. The method uses an iterative method to exploit the low rank feature of the Boltzmannized flux operator and subsequently only propagates the eigenvectors that have significant contributions to the rate constant. In the present article, this method is used to calculate the thermal rate constants of the Cl+H{sub 2}{r_arrow}HCl+H reaction in the temperature range of 200{endash}1500{degree}K. Total angular momentum is treated by employing the body-fixed axis frame, both exactly and also via various approximations. Comparisons with previous exact and approximate theoretical results are made. {copyright} {ital 1997 American Institute of Physics.}

• Research Organization: Lawrence Berkeley National Laboratory
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 553986
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 107; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ANGULAR MOMENTUM
CHEMICAL REACTION KINETICS
CHLORINE
CORRELATION FUNCTIONS
EIGENFUNCTIONS
EIGENVALUES
HYDROGEN
TEMPERATURE RANGE 0065-0273 K
TEMPERATURE RANGE 0273-0400 K
TEMPERATURE RANGE 0400-1000 K
TEMPERATURE RANGE 1000-4000 K