Electron-mediated phonon-phonon coupling drives the vibrational relaxation of CO on Cu(100)

Abstract

We bring forth a consistent theory for the electron-mediated vibrational intermode coupling that clarifies the microscopic mechanism behind the vibrational relaxation of adsorbates on metal surfaces. Our analysis points out the inability of state-of-the-art nonadiabatic theories to quantitatively reproduce the experimental linewidth of the CO internal stretch mode on Cu(100) and it emphasizes the crucial role of the electron-mediated phonon-phonon coupling in this regard. The results demonstrate a strong electron-mediated coupling between the internal stretch and low-energy CO modes, but also a significant role of surface motion. Our nonadiabatic theory is also able to explain the temperature dependence of the internal stretch phonon linewidth, thus far considered a sign of the direct anharmonic coupling.

arXiv commentArticle as accepted for publication in Physical Review Letters

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• 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
• Electron-mediated anharmonicity and its role in the Raman spectrum of graphene
• Enhanced Phonon-Phonon Interactions and Weakened Electron-Phonon Coupling in Charge-Density-Wave Topological Semimetal EuAl4 with a Possible Intermediate Electronic State
• Anomalous transient blueshift in the internal stretch mode of CO/Pd(111)
• Vibrational Energy Dissipation in Non-Contact Single-Molecule Junctions Governed by Local Geometry and Electronic Structure
• Asymmetry and coverage dependence in two-pulse correlation measurements of CO photodesorption from Pd(111): Insights from theory