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Author Spath, B. W. ♦ Miller, W. H.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword CHEMISTRY ♦ CHEMICAL REACTION KINETICS ♦ SEMICLASSICAL APPROXIMATION ♦ DEGREES OF FREEDOM ♦ GREEN FUNCTION ♦ ONE-DIMENSIONAL CALCULATIONS ♦ PROBABILISTIC ESTIMATION
Abstract It is shown how the rigorous quantum mechanical expression for the cumulative reaction probability (CRP) obtained by Seideman and Miller [J. Chem. Phys. {bold 96}, 4412; {bold 97}, 2499 (1992)], {ital N}({ital E})=4tr[{epsilon}{cflx char}{sub {ital r}}{center_dot}{ital G}{cflx char}{asterisk}({ital E}){center_dot}{epsilon}{cflx char}{sub {ital p}}{center_dot}{ital G}{cflx char}({ital E})], which has been the basis for quantum calculations of the CRP for simple chemical reactions, can also be utilized with a semiclassical approximation for the Green{close_quote}s function, {ital G}{cflx char}({ital E}){identical_to}({ital E}+{ital i}{epsilon}{cflx char}-{ital H}{cflx char}){sup -1}=({ital i}{Dirac_h}){sup -1}{integral}{sup {infinity}}{sub 0} exp({ital iEt}/{Dirac_h})exp(-{ital i}({ital H}{cflx char}-{ital i}{epsilon}{cflx char}){ital t}/{Dirac_h}). Specifically, a modified Filinov transformation of an initial value representation of the semiclassical propagator has been used to approximate the Green{close_quote}s function. Numerical application of this trajectory-based semiclassical approximation to a simple one-dimensional (barrier transmission) test problem shows the approach to be an accurate description of the reaction probability, even some ways into the tunneling regime. {copyright} {ital 1996 American Institute of Physics.}
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 1996-01-01
Publisher Department Lawrence Berkeley National Laboratory
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 104
Issue Number 1
Organization Lawrence Berkeley National Laboratory


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