Nuclear dynamics at molecule-metal interfaces: A pseudoparticle perspective

TL;DR

This paper presents a pseudoparticle-based approach to model nuclear dynamics at molecule-metal interfaces, capturing non-adiabatic effects and bridging surface hopping and Ehrenfest dynamics depending on coupling strength.

Contribution

It introduces a gradient expansion method that simplifies the complex many-body pseudoparticle formulation into a semi-classical framework while preserving non-adiabatic electronic effects.

Findings

Reproduces surface hopping dynamics in weak coupling limit

Recovers Ehrenfest dynamics in strong coupling regime

Provides a unified approach for different coupling strengths

Abstract

We discuss nuclear dynamics at molecule-metal interfaces including non-equilibrium molecular junctions. Starting from the many-body states (pseudoparticle) formulation of the molecule-metal system in the molecular vibronic basis, we introduce gradient expansion in order to reduce the adiabatic nuclear dynamics (that is, nuclear dynamics on a single molecular potential surface) into its semi-classical form while maintaining the effect of the non-adiabatic electronic transitions between different molecular charge states. This yields a set of equations for the nuclear dynamics in the presence of these non-adiabatic transitions, which reproduce 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, which is relevant when this coupling is strong.