title: Fewest Switches Surface Hopping in Liouville Space.
abstract: The novel approach to nonadiabatic quantum dynamics greatly increases the accuracy of the most popular semiclassical technique while maintaining its simplicity and efficiency. Unlike the standard Tully surface hopping in Hilbert space, which deals with population flow, the new strategy in Liouville space puts population and coherence on equal footing. Dual avoided crossing and energy transfer models show that the accuracy is improved in both diabatic and adiabatic representations and that Liouville space simulation converges faster with the number of trajectories than Hilbert space simulation. The constructed master equation accurately captures superexchange, tunneling, and quantum interference. These effects are essential for charge, phonon and energy transport and scattering, exciton fission and fusion, quantum optics and computing, and many other areas of physics and chemistry.
authors.affiliation: Department of Chemistry, University of Southern California , 3620 McClintock Avenue, Los Angeles, California 90089-1062, United States.
authors.forename: Linjun
authors.initials: L
authors.lastname: Wang
authors.affiliation: Department of Physics and Astronomy, University of Southern California , 825 Bloom Walk, Los Angeles, California 90089-0485, United States.
authors.forename: Andrew E
authors.initials: AE
authors.lastname: Sifain
authors.affiliation: Department of Chemistry, University of Southern California , 3620 McClintock Avenue, Los Angeles, California 90089-1062, United States.
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Prezhdo
keywords: Liouville space; quantum coherence and interference; superexchange; surface hopping; tunneling