Ab initio calculation of electron-phonon linewidths and molecular dynamics with electronic friction at metal surfaces with numeric atom-centred orbitals

Abstract

Molecular motion at metallic surfaces is affected by nonadiabatic effects and electron-phonon coupling. The ensuing energy dissipation and dynamical steering effects are not captured by classical molecular dynamics simulations, but can be described with the molecular dynamics with electronic friction method and linear response calculations based on density functional theory. Herein, we present an implementation of electron-phonon response based on an all-electron numeric atomic orbital description in the electronic structure code FHI-aims. After providing details of the underlying approximations and numerical considerations, we present significant scalability and performance improvements of the new code compared to a previous implementation (Maurer et al 2016 Phys. Rev. B 94 115432). We compare convergence behaviour and results of our simulations for exemplary systems such as H2 adsorption on Cu(111), and CO on Ru(0001) against existing plane wave implementations. We examine different expressions to calculate electronic friction and vibrational lifetimes for their reliability and ease of convergence. Finally, we show the capabilities of the new code by studying the contribution of interband and intraband excitations to the vibrational lifetime of aperiodic adsorbate motion in large, previously unfeasible, periodic surface models.