title: Non-adiabatic dynamics close to conical intersections and the surface hopping perspective.
abstract: Conical intersections play a major role in the current understanding of electronic de-excitation in polyatomic molecules, and thus in the description of photochemistry and photophysics of molecular systems. This article reviews aspects of the basic theory underlying the description of non-adiabatic transitions at conical intersections, with particular emphasis on the important case when the dynamics of the nuclei are treated classically. Within this classical nuclear motion framework, the main aspects of the surface hopping methodology in the conical intersection context are presented. The emerging picture from this treatment is that of electronic transitions around conical intersections dominated by the interplay of the nuclear velocity and the derivative non-adiabatic coupling vector field.
authors.affiliation: Department of Chemistry, Imperial College London UK.
authors.forename: João Pedro
authors.initials: JP
authors.lastname: Malhado
authors.affiliation: Department of Chemistry, Imperial College London UK.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Bearpark
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado, Boulder Boulder, CO, USA ; Département de Chimie, École Normale Supérieur, UMR ENS-CNRS-UPMC 8640 Paris, France.
authors.forename: James T
authors.initials: JT
authors.lastname: Hynes
keywords: Born-Oppenheimer approximation; Landau-Zener; conical intersections; decoherence; non-adiabatic dynamics; surface hopping