CO Stretch Vibration Lives Long on Au(111)

Lončarić, Ivor; Alducin, M.; Juaristi, J. I.; Novko, Dino (2019) CO Stretch Vibration Lives Long on Au(111). Journal of Physical Chemistry Letters, 10 . pp. 1043-1047. ISSN 1948-7185

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Abstract

Measured lifetimes of the CO internal stretch mode on various metal surfaces routinely lie in the picosecond regime. These short vibrational lifetimes, which are actually reproduced by current first-principles nonadiabatic calculations, are attributed to the rapid vibrational energy loss that is caused by the facile excitation of electron–hole pairs in metals. However, this explanation was recently questioned by the huge discrepancy that exists for CO on Au(111) between the experimental vibrational lifetime that is larger than 100 ps and the previous theoretical predictions of 4.8 and 1.6 ps. Here, we show that the state-of-the- art nonadiabatic theory does reproduce the long CO lifetime measured in Au(111) provided the molecule–surface interaction is properly described. Importantly, our new results confirm that the current understanding of the adsorbates’ vibrational relaxation at metal surfaces is indeed valid.

Item Type:	Article
Additional Information:	I.L. was supported by the European Union through the European Regional Development Fund, the Competitiveness and Cohesion Operational Programme (KK.01.1.1.06) and the H2020 CSA Twinning Project 692194, RBI-T-WINNING. We acknowledge the Spanish Ministerio de Economia, Industria y Competitividad Grant FIS2016-76471-P. D.N. acknowledges financial support from the European Regional Development Fund for the "Center of Excellence for Advanced Materials and Sensing Devices" (Grant KK.01.1.1.01.0001). Computational resources were provided by the Donostia International Physics Center (DIPC) computing center.
Uncontrolled Keywords:	density functional perturbation theory ; van der Waals functionals
Subjects:	NATURAL SCIENCES > Physics
Divisions:	Theoretical Physics Division
Projects:	Project title Project leader Project code Project type Ruđer Bošković Institute: Twinning for a step forward of the Theoretical Physics Division-RBI-T-WINNING Fabrizio NESTI 692194 EK UNSPECIFIED UNSPECIFIED ZCI QuantixLie UNSPECIFIED
Depositing User:	Ivor Lončarić
Date Deposited:	20 Nov 2019 15:51
URI:	http://fulir.irb.hr/id/eprint/5096
DOI:	10.1021/acs.jpclett.9b00069

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• CO Stretch Vibration Lives Long on Au(111) (deposited 19 Nov 2019 12:10)
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