Semiclassical theory of electronically nonadiabatic dynamics: Results of a linearized approximation to the initial value representation
- Department of Chemistry, University of , California (United States)
A linearized approximation to the semiclassical initial value representation (SC-IVR), referred to herein as the LSC-IVR, was used by us in a recent paper [J. Chem. Phys. {bold 108}, 9726 (1998)] to calculate reactive flux correlation functions for a model of a chemical reaction on a single potential energy surface. This paper shows how the LSC-IVR{emdash}which is much easier to apply than the full SC-IVR because it linearizes the phase difference between interfering classical trajectories{emdash}can be applied to {ital electronically nonadiabatic} processes, i.e., those involving transitions between different potential-energy surfaces. Applications to several model problems are presented to show its usefulness: These are the nonadiabatic scattering problems used by Tully to test surface-hopping models, and also the spin{endash}boson model of coupled electronic states in a condensed phase environment. Though not as accurate as the full SC-IVR, the LSC-IVR does a reasonably good job for all these applications, even describing correctly Stuckelberg oscillations (interference between nonadiabatic transitions) and the transition between coherent and incoherent behavior in the spin{endash}boson example. {copyright} {ital 1998 American Institute of Physics.} thinsp
- OSTI ID:
- 662192
- Journal Information:
- Journal of Chemical Physics, Vol. 109, Issue 17; Other Information: PBD: Nov 1998
- Country of Publication:
- United States
- Language:
- English
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