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Electron-hole-pair-induced vibrational energy relaxation of rhenium catalysts on gold surfaces
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Ge, Aimin, Rudshteyn, Benjamin, Zhu, Jingyi, Maurer, Reinhard J., Batista, Victor S. and Lian, Tianquan (2018) Electron-hole-pair-induced vibrational energy relaxation of rhenium catalysts on gold surfaces. Journal of Physical Chemistry Letters, 9 (2). pp. 406-412. doi:10.1021/acs.jpclett.7b02885 ISSN 1948-7185.
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Official URL: http://doi.org/10.1021/acs.jpclett.7b02885
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)3Cl (Re(CO)3Cl) 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)3Cl adsorbate into the gold surface occurs at the same timescale as IVR of Re(CO)3Cl in aprotic solvents. Therefore, it is expected to be particularly relevant to understanding the reduced catalytic activity of the homogeneous catalyst when anchored on a metal surface.
Item Type: | Journal Article | |||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||
Library of Congress Subject Headings (LCSH): | Vibrational spectra, Molecular relaxation, Molecular dynamics, Perturbation (Quantum dynamics), Energy transfer | |||||||||
Journal or Publication Title: | Journal of Physical Chemistry Letters | |||||||||
Publisher: | American Chemical Society | |||||||||
ISSN: | 1948-7185 | |||||||||
Official Date: | 18 January 2018 | |||||||||
Dates: |
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Volume: | 9 | |||||||||
Number: | 2 | |||||||||
Page Range: | pp. 406-412 | |||||||||
DOI: | 10.1021/acs.jpclett.7b02885 | |||||||||
Status: | Peer Reviewed | |||||||||
Publication Status: | Published | |||||||||
Access rights to Published version: | Restricted or Subscription Access | |||||||||
Date of first compliant deposit: | 12 December 2017 | |||||||||
Date of first compliant Open Access: | 13 December 2017 | |||||||||
RIOXX Funder/Project Grant: |
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