Non-Adiabatic Vibrational Damping of Molecular Adsorbates: Insights into Electronic Friction and the Role of Electronic Coherence

Abstract

We present a perturbation approach rooted in time-dependent density-functional theory to calculate electron hole (eh)-pair excitation spectra during the non-adiabatic vibrational damping of adsorbates on metal surfaces. Our analysis for the benchmark systems CO on Cu(100) and Pt(111) elucidates the surprisingly strong influence of rather short electronic coherence times. We demonstrate how in the limit of short electronic coherence times, as implicitly assumed in prevalent quantum nuclear theories for the vibrational lifetimes as well as electronic friction, band structure effects are washed out. Our results suggest that more accurate lifetime or chemicurrent-like experimental measurements could characterize the electronic coherence.

arXiv commentArticle as accepted for publication in Physical Review Letters

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Cited by in corpus (6)

• Electron-mediated phonon-phonon coupling drives the vibrational relaxation of CO on Cu(100)
• Ultrafast Transient Dynamics of Adsorbates on Surfaces Deciphered: The Case of CO on Cu(100)
• Adiabatic and Nonadiabatic Energy Dissipation during Scattering of Vibrationally Excited CO from Au(111)
• Electronic friction coefficients from the atom-in-jellium model for $Z=1-92$
• Vibrational dynamics of CO on Pd(111) in and out of thermal equilibrium
• Nonadiabatic dynamics at metal surfaces: fewest switches surface hopping with electronic relaxation