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

Aimin Ge, Benjamin Rudshteyn, Jingyi Zhu, Reinhard J. Maurer, Victor S. Batista, Tianquan Lian

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18 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)406-412
Number of pages7
JournalJournal of Physical Chemistry Letters
Issue number2
Publication statusPublished - 2018 Jan 18
Externally publishedYes

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry


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