Nuclear Dynamics at Molecule-Metal Interfaces: A Pseudoparticle Perspective

Michael Galperin*, Abraham Nitzan

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Pages (from-to)4898-4903
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume6
Issue number24
DOIs
StatePublished - 20 Nov 2015

Keywords

  • Ehrenfest dynamics
  • molecule-metal interface
  • surface-hopping formulation

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