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

TL;DR

This paper improves the calculation of vibrational lifetimes of diatomic molecules on metal surfaces by incorporating intra-molecular effects, leading to better agreement with experimental data and enhancing ab initio molecular dynamics simulations.

Contribution

It introduces an AIM-based charge partitioning scheme within the LDFA to accurately account for intra-molecular contributions in electronic friction calculations.

Findings

Enhanced accuracy of vibrational damping rates with AIM scheme

Quantitative agreement with experimental and theoretical benchmarks

Reliable approach for electronic dissipation in surface reactions

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.