Ab-initio tensorial electronic friction for molecules on metal surfaces: nonadiabatic vibrational relaxation

Abstract

Molecular adsorbates on metal surfaces exchange energy with substrate phonons and low-lying electron-hole pair excitations. In the limit of weak coupling, electron-hole pair excitations can be seen as exerting frictional forces on adsorbates that enhance energy transfer and facilitate vibrational relaxation or hot-electron mediated chemistry. We have recently reported on the relevance of tensorial properties of electronic friction [Phys. Rev. Lett. 116, 217601 (2016)] in dynamics at surfaces. Here we present the underlying implementation of tensorial electronic friction based on Kohn-Sham Density Functional Theory for condensed phase and cluster systems. Using local atomic-orbital basis sets, we calculate nonadiabatic coupling matrix elements and evaluate the full electronic friction tensor in the classical limit. Our approach is numerically stable and robust as shown by a detailed convergence analysis. We furthermore benchmark the accuracy of our approach by calculation of vibrational relaxation rates and lifetimes for a number of diatomic molecules at metal surfaces. We find friction-induced mode-coupling between neighboring CO adsorbates on Cu(100) in a c(2x2) overlayer to be important to understand experimental findings.

16 pages, 8 figures, accepted to Physical Review B

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• Vibrational Relaxation at a Metal Surface: Electronic Friction Versus Classical Master Equations
• Efficient implementation and performance analysis of the independent electron surface hopping method for dynamics at metal surfaces
• Electronic friction in interacting systems
• Electronic friction coefficients from the atom-in-jellium model for $Z=1-92$
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory II: Benchmarks and Applications
• Nonadiabatic dynamics at metal surfaces: fewest switches surface hopping with electronic relaxation
• NQCDynamics.jl: A Julia Package for Nonadiabatic Quantum Classical Molecular Dynamics in the Condensed Phase