Path integral formulation for quantum nonadiabatic dynamics and the mixed quantum classical limit
Year: 2007
Type: article
Abstract: This work identifies geometric effects on dynamics due to nonadiabatic couplings in Born-Oppenheimer systems and provides a systematic method for deriving corrections to mixed quantum classical methods. Specifically, an exact path integral formulation of the quantum nonadiabatic dynamics of Born-Oppenheimer systems is described. Stationary phase approximations to the propagator for full quantum dynamics are derived. It is shown that quantum corrections to mixed quantum classical methods can be obtained through stationary phase approximations to the full quantum dynamics. A rigorous description of the quantum corrections due to electronic nonadiabatic coupling on the nuclear dynamics within the Ehrenfest framework is obtained. The fewest switches surface hopping method is shown to be obtained as a quasiclassical approximation to the dynamics, and natural semiclassical extensions to include classically forbidden nonadiabatic transitions are suggested.
Source: The Journal of Chemical Physics
DOI: 10.1063/1.2716387
Author: Vinod Krishna
Institution: Yale University
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W2070217548