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Title: Electron–Hole-Pair-Induced Vibrational Energy Relaxation of Rhenium Catalysts on Gold Surfaces

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 on the same time scale 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 to a metal surface.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States
  2. Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States; Yale Energy Sciences Institute, Yale University, West Haven, Connecticut 06516, United States
  3. Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States; Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, United Kingdom
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE
OSTI Identifier:
1484252
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Ge, Aimin, Rudshteyn, Benjamin, Zhu, Jingyi, Maurer, Reinhard J., Batista, Victor S., and Lian, Tianquan. Electron–Hole-Pair-Induced Vibrational Energy Relaxation of Rhenium Catalysts on Gold Surfaces. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.7b02885.
Ge, Aimin, Rudshteyn, Benjamin, Zhu, Jingyi, Maurer, Reinhard J., Batista, Victor S., & Lian, Tianquan. Electron–Hole-Pair-Induced Vibrational Energy Relaxation of Rhenium Catalysts on Gold Surfaces. United States. doi:10.1021/acs.jpclett.7b02885.
Ge, Aimin, Rudshteyn, Benjamin, Zhu, Jingyi, Maurer, Reinhard J., Batista, Victor S., and Lian, Tianquan. Wed . "Electron–Hole-Pair-Induced Vibrational Energy Relaxation of Rhenium Catalysts on Gold Surfaces". United States. doi:10.1021/acs.jpclett.7b02885.
@article{osti_1484252,
title = {Electron–Hole-Pair-Induced Vibrational Energy Relaxation of Rhenium Catalysts on Gold Surfaces},
author = {Ge, Aimin and Rudshteyn, Benjamin and Zhu, Jingyi and Maurer, Reinhard J. and Batista, Victor S. and Lian, Tianquan},
abstractNote = {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 on the same time scale 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 to a metal surface.},
doi = {10.1021/acs.jpclett.7b02885},
journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 2,
volume = 9,
place = {United States},
year = {2018},
month = {1}
}