Electronic friction-based vibrational lifetimes of molecular adsorbates: Beyond the independent atom approximation

Abstract

We assess the accuracy of vibrational damping rates of diatomic adsorbates on metal surfaces as calculated within the local-density friction approximation (LDFA). An atoms-in-molecules (AIM) type charge partitioning scheme accounts for intra-molecular contributions and overcomes the systematic underestimation of the non-adiabatic losses obtained within the prevalent independent atom approximation. The quantitative agreement obtained with theoretical and experimental benchmark data suggests the LDFA-AIM as an efficient and reliable approach to account for electronic dissipation in ab initio molecular dynamics simulations of surface chemical reactions.

5 pages including 2 figures

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• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory
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• An Antisymmetric Berry Frictional Force At Equilibrium in the Presence of Spin-Orbit Coupling
• Nonadiabatic dynamics at metal surfaces: fewest switches surface hopping with electronic relaxation