Collisional recombination reaction H+O{sub 2}+M{r_arrow}HO{sub 2}+M: Quantum mechanical study using filter diagonalization

Journal Article · Mon Jul 01 04:00:00 EDT 1996 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.471903· OSTI ID:285551

Mandelshtam, V A; Taylor, H S ^[1]; Miller, W H ^[2]

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1. Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482 (United States)
2. Department of Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

We report the results of calculations for the collisional recombination rate of the reaction H+O{sub 2}+M{r_arrow}HO{sub 2}+M. This study uses the recently developed quantum mechanical theory of recombination (within the strong collision approximation) based on the flux{endash}flux correlation function analysis [J. Phys. Chem. {bold 99}, 12387 (1995)]. The quantum dynamics calculations are based on the new very efficient computational procedure of filter diagonalization [J. Chem. Phys. {bold 103}, 10074 (1995)]. This procedure allows one to obtain individual complex eigenenergies and eigenfunctions of a large non-Hermitian matrix representation of the Hamiltonian with an absorbing potential. The computed rates are compared to the Lindemann steady-state approximation result. The latter leads to an overestimation of the rate since it does not take into account the resonance interference effects. This becomes more critical at higher temperatures where many broad high energy overlapping resonances contribute to the rate. {copyright} {ital 1996 American Institute of Physics.}

• Research Organization: Lawrence Berkeley National Laboratory
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 285551
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 105; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
66 PHYSICS
ATOM-MOLECULE COLLISIONS
CALCULATION METHODS
CHEMICAL REACTION KINETICS
CORRELATION FUNCTIONS
HAMILTONIANS
HERMITIAN OPERATORS
POTENTIAL ENERGY SURFACES
QUANTUM MECHANICS
REACTION RATES
RECOMBINATION