title: Nuclear Dynamics at Molecule-Metal Interfaces: A Pseudoparticle Perspective.
abstract: We discuss nuclear dynamics at molecule-metal interfaces including nonequilibrium molecular junctions. Starting from the many-body states (pseudoparticle) formulation of the molecule-metal system in the molecular vibronic basis, we introduce gradient expansion to reduce the adiabatic nuclear dynamics (that is, nuclear dynamics on a single molecular potential surface) into its semiclassical form while maintaining the effect of the nonadiabatic electronic transitions between different molecular charge states. This yields a set of equations for the nuclear dynamics in the presence of these nonadiabatic transitions, which reproduce the surface-hopping formulation in the limit of small metal-molecule coupling (where broadening of the molecular energy levels can be disregarded) and Ehrenfest dynamics (motion on the potential of mean force) when information on the different charging states is traced out.
authors.affiliation: Department of Chemistry and Biochemistry, University of California at San Diego , La Jolla, California 92093, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Galperin
authors.affiliation: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.|School of Chemistry, Tel Aviv University , Tel Aviv, 69978, Israel.
authors.forename: Abraham
authors.initials: A
authors.lastname: Nitzan
keywords: Ehrenfest dynamics; molecule−metal interface; surface-hopping formulation