Electronic Friction-Based Vibrational Lifetimes of Molecular Adsorbates: Beyond the Independent-Atom Approximation

Simon P. Rittmeyer, Jörg Meyer, J. Iñaki Juaristi, and Karsten Reuter

Phys. Rev. Lett. 115, 046102 – Published 21 July 2015

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.

Received 8 December 2014

DOI:https://doi.org/10.1103/PhysRevLett.115.046102

Authors & Affiliations

Simon P. Rittmeyer^1,*, Jörg Meyer^2,†, J. Iñaki Juaristi^3,4,5, and Karsten Reuter¹

¹Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany
²Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, Netherlands
³Departamento de Física de Materiales, Facultad de Químicas, UPV/EHU, Apartado 1072, 20080 San Sebastián, Spain
⁴Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain
⁵Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain

^*Corresponding author. simon.rittmeyer@tum.de
^†j.meyer@chem.leidenuniv.nl

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Issue

Vol. 115, Iss. 4 — 24 July 2015

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