Nonseparable transition state theory for nonzero total angular momentum: Implications for {ital J} shifting and application to the OH+H{sub 2} reaction
- Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322 (United States)
We report vibration/rotation energies of the OHH{sub 2} transition state using the code {open_quotes}Multimode,{close_quotes} for total angular momentum J=0, 1, and 4. Rotation is treated in the adiabatic rotation approximation for J=1 and 4, as well as exactly, i.e., including Coriolis coupling, for J=1. State-dependent rotation constants are obtained using the adiabatic rotation energies from the J=0 and 1 calculations and shown to predict accurately the adiabatic rotation rovibrational energies for J=4. These rotation constants are used in new {ital J}-shifting calculations of the thermal rate constant for the reaction OH+H{sub 2}{r_arrow}H{sub 2}O+H using results from a previous accurate calculation of the rate constant for J=0 [U. Manthe, T. Seideman, and W. H. Miller, J. Chem. Phys. {bold 99}, 10078 (1993); {bold 101}, 4759 (1994)]. Comparisons with previous {ital J}-shifting and recent centrifugal sudden calculations of the rate constant [D. H. Zhang, J. C. Light, and S-Y. Lee, J. Chem. Phys. {bold 109}, 79 (1998)] of this reaction are presented. A modification of the previous centrifugal sudden rate constant is made and shown to yield results that are in good agreement with the new {ital J}-shifting calculations. Finally, an assessment of Coriolis coupling is made. {copyright} {ital 1999 American Institute of Physics.}
- OSTI ID:
- 321482
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 110; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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