title: 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 intramolecular contributions and overcomes the systematic underestimation of the nonadiabatic losses obtained within the prevalent independent-atom approximation. The quantitative agreement obtained with theoretical and experimental benchmark data suggests the LDFA-AIM scheme as an efficient and reliable approach to account for electronic dissipation in ab initio molecular dynamics simulations of surface chemical reactions.
authors.affiliation: Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany.
authors.forename: Simon P
authors.initials: SP
authors.lastname: Rittmeyer
authors.affiliation: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, Netherlands.
authors.forename: Jörg
authors.initials: J
authors.lastname: Meyer
authors.affiliation: Departamento de Física de Materiales, Facultad de Químicas, UPV/EHU, Apartado 1072, 20080 San Sebastián, Spain.|Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.|Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
authors.forename: J Iñaki
authors.initials: JI
authors.lastname: Juaristi
authors.affiliation: Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany.
authors.forename: Karsten
authors.initials: K
authors.lastname: Reuter