Memory-dependent electronic friction for nonadiabatic dynamics at metal surfaces

Abstract

Electronic excitation induced by nuclear motion is a key energy dissipation channel in chemical dynamics at metal surfaces. Here, nonadiabatic effects can be treated via molecular dynamics with electronic friction, where they act as frictional drag and fluctuation force contributions. Commonly, the Markov approximation is imposed, so memory effects are ignored. A theoretical formalism is presented to evaluate tensorial and configuration-dependent electronic friction memory kernels from first principles. We evaluate friction kernels for Newns--Anderson Hamiltonian models as well as within Kohn--Sham density functional theory and analyse their mathematical properties and configuration dependence. For hyperthermal atomic and diatomic scattering, memory effects arising from frequency and configuration dependence of electronic friction affect energy exchange between adsorbate and metal electrons. Memory effects lead to an increase of vibrational and a reduction of translational energy loss in the case of nitric oxide scattering on Au(111), leading to an increase of directional anisotropy of friction. Importantly, memory-dependent evaluation of electronic friction removes the need to define a single effective Markovian friction coefficient from the structured frequency-dependent electronic response.