Quantum calculation of the recombination rate constant of H + CO {yields} HCO

Journal Article · Thu Sep 12 04:00:00 EDT 1996 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/jp961292m· OSTI ID:380878

Qi, J; Bowman, J M ^[1]

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1. Emory Univ., Atlanta, GA (United States)

The rate constant for the recombination reaction H + CO + M {yields} HCO + M is obtained at four temperatures as a function of the collision frequency using a theory recently proposed by Miller. This theory combines the flux-flux correlation function with the classical strong collision assumption to obtain the recombination rate constant as a function of the collision frequency. The expression for the rate constant is evaluated in a basis of complex L{sup 2} eigenfunctions of a complex Hamiltonian, given by the real Hamiltonian for the nonrotating HCO system (J = 0), plus an absorbing potential in the asymptotic potential. The J-shifting approximation is used to obtain the rate constant for non-zero J. The flux-flux correlation function is evaluated at several dividing surfaces, which define the boundary of the complex, and only a fairly minor dependence on this surface is found at low temperatures, but a more substantial dependence is found at high T. The results are compared with those of the standard Lindemann theory and in the low-pressure region with the low-pressure limit of the Lindemann theory. The calculated results are compared with experiment at room temperature, with Ar as the buffer gas, and can be made to agree well with experiment if the total stabilization collision cross section is about 15 bohr{sup 2}. 31 refs., 6 figs., 1 tab.

• DOE Contract Number: FG05-86ER13568
• OSTI ID: 380878
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 37 Vol. 100; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
99 GENERAL AND MISCELLANEOUS
CALCULATION METHODS
CARBON MONOXIDE
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
HAMILTONIANS
HYDROGEN
MATHEMATICAL MODELS
RECOMBINATION