On the Breakdown of the Ehrenfest Method for Molecular Dynamics on Surfaces

Abstract

Due to a continuum of electronic states present in periodic systems, the description of molecular dynamics on surfaces poses a serious computational challenge. One of the most used families of approaches in these settings are friction theories, which are based on the Ehrenfest (EH) approach. Yet, a mean-field treatment of electronic degrees of freedom in the EH method makes this approach inaccurate in some cases. Our aim is to clarify when EH breaks down for molecular dynamics on surfaces. Answering this question provides limits of applicability for more approximate friction theories derived from EH. We assess the EH method on one-dimensional, numerically exactly solvable models with a large but finite number of electronic states. Using the Landau-Zener formula and the Massey parameter, an expression that determines when EH breaks down is deduced.

References in corpus (4)

• Born-Oppenheimer Dynamics, Electronic Friction, and the Inclusion of Electron-Electron Interactions
• Mode specific electronic friction in dissociative chemisorption on metal surfaces: H${}_2$ on Ag(111)
• Electronic friction near metal surfaces: a case where molecule-metal couplings depend on nuclear coordinates
• Mixed quantum-classical dynamics using collective electronic variables: A better alternative to electronic friction theories