Resonances in the cumulative reaction probability for a model electronically nonadiabatic reaction
- Department of Chemistry and Cherry L. Emerson Center for Science Computation, Emory University, Atlanta, Georgia 30322 (United States)
The cumulative reaction probability, flux{endash}flux correlation function, and rate constant are calculated for a model, two-state, electronically nonadiabatic reaction, given by Shin and Light [S. Shin and J. C. Light, J. Chem. Phys. {bold 101}, 2836 (1994)]. We apply straightforward generalizations of the flux matrix/absorbing boundary condition approach of Miller and co-workers to obtain these quantities. The upper adiabatic electronic potential supports bound states, and these manifest themselves as {open_quote}{open_quote}recrossing{close_quote}{close_quote} resonances in the cumulative reaction probability, at total energies above the barrier to reaction on the lower adiabatic potential. At energies below the barrier, the cumulative reaction probability for the coupled system is shifted to higher energies relative to the one obtained for the ground state potential. This is due to the effect of an additional effective barrier caused by the nuclear kinetic operator acting on the ground state, adiabatic electronic wave function, as discussed earlier by Shin and Light. Calculations are reported for five sets of electronically nonadiabatic coupling parameters. {copyright} {ital 1996 American Institute of Physics.}
- DOE Contract Number:
- FG05-86ER13568
- OSTI ID:
- 283805
- Journal Information:
- Journal of Chemical Physics, Vol. 104, Issue 19; Other Information: PBD: May 1996
- Country of Publication:
- United States
- Language:
- English
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