Universität zu Köln

Ge, Aimin ORCID: 0000-0003-0127-3193, Rudshteyn, Benjamin ORCID: 0000-0002-9511-6780, Zhu, Jingyi, Maurer, Reinhard J., Batista, Victor S. and Lian, Tianquan ORCID: 0000-0002-8351-3690 (2018). Electron-Hole-Pair-Induced Vibrational Energy Relaxation of Rhenium Catalysts on Gold Surfaces. J. Phys. Chem. Lett., 9 (2). S. 406 - 413. WASHINGTON: AMER CHEMICAL SOC. ISSN 1948-7185

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Abstract

A combination of time-resolved vibrational spectroscopy and density functional theory techniques have been applied to study the vibrational energy relaxation dynamics of the Re(4,4'-dicyano-2,2'-bipyridine)(CO)(3)Cl (Re(CO)(3)Cl) catalyst for CO2 to CO conversion bound to gold surfaces. The kinetics of vibrational relaxation exhibits a biexponential decay including an ultrafast initial relaxation and complete recovery of the ground vibrational state. Ab initio molecular dynamics simulations and time-dependent perturbation theory reveal the former to be due to vibrational population exchange between CO stretching modes and the latter to be a combination of intramolecular vibrational relaxation (IVR) and electron-hole pair (EHP)-induced energy transfer into the gold substrate. EHP-induced energy transfer from the Re(CO)(3)Cl adsorbate into the gold surface occurs on the same time scale as IVR of Re(CO)(3)Cl in aprotic solvents. Therefore, it is expected to be particularly relevant to understanding the reduced catalytic activity of the homogeneous catalyst when anchored to a metal surface.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Ge, Aimin UNSPECIFIED orcid.org/0000-0003-0127-3193 UNSPECIFIED Rudshteyn, Benjamin UNSPECIFIED orcid.org/0000-0002-9511-6780 UNSPECIFIED Zhu, Jingyi UNSPECIFIED UNSPECIFIED UNSPECIFIED Maurer, Reinhard J. UNSPECIFIED UNSPECIFIED UNSPECIFIED Batista, Victor S. UNSPECIFIED UNSPECIFIED UNSPECIFIED Lian, Tianquan UNSPECIFIED orcid.org/0000-0002-8351-3690 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-198704
DOI:	10.1021/acs.jpclett.7b02885
Journal or Publication Title:	J. Phys. Chem. Lett.
Volume:	9
Number:	2
Page Range:	S. 406 - 413
Date:	2018
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1948-7185
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language WATER-OXIDATION; CARBON-DIOXIDE; ELECTROCATALYTIC REDUCTION; CO2 REDUCTION; MOLECULAR MONOLAYERS; STRUCTURAL DYNAMICS; SPECTROSCOPY; GENERATION; IMMOBILIZATION; APPROXIMATION Multiple languages Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, Multidisciplinary; Physics, Atomic, Molecular & Chemical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/19870