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A closer look into the distance dependence of vibrational energy transfer on surfaces using 2D IR spectroscopy


Fernández-Terán, Ricardo; Hamm, Peter (2020). A closer look into the distance dependence of vibrational energy transfer on surfaces using 2D IR spectroscopy. Journal of Chemical Physics, 153(15):154706.

Abstract

Vibrational energy transfer (VET) between two isotopologues of [Re(dcb)(CO)3Br] immobilized on a TiO2 surface is studied with the help of 2D IR spectroscopy in dependence of surface coverage. To dilute the molecules on the surface, and thereby control the intermolecular distances, two different diluents have been used: a third isotopologue of the same molecule and 4-cyanobenzoic acid. As expected, the VET rate decreases with dilution. For a quantitative investigation of the distance dependence of the VET rate, we analyze the data based on an excitonic model. This model reveals the typical 1/r6-distance dependence for a dimer of a donor and acceptor, similar to the nuclear Overhauser effect in NMR spectroscopy or Förster resonant energy transfer in electronic spectroscopy. However, VET becomes a collective phenomenon on the surface, with the existence of a network of coupled molecules and its disappearance below a percolation threshold, dominating the concentration dependence of the VET rate.

Abstract

Vibrational energy transfer (VET) between two isotopologues of [Re(dcb)(CO)3Br] immobilized on a TiO2 surface is studied with the help of 2D IR spectroscopy in dependence of surface coverage. To dilute the molecules on the surface, and thereby control the intermolecular distances, two different diluents have been used: a third isotopologue of the same molecule and 4-cyanobenzoic acid. As expected, the VET rate decreases with dilution. For a quantitative investigation of the distance dependence of the VET rate, we analyze the data based on an excitonic model. This model reveals the typical 1/r6-distance dependence for a dimer of a donor and acceptor, similar to the nuclear Overhauser effect in NMR spectroscopy or Förster resonant energy transfer in electronic spectroscopy. However, VET becomes a collective phenomenon on the surface, with the existence of a network of coupled molecules and its disappearance below a percolation threshold, dominating the concentration dependence of the VET rate.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Physics and Astronomy
Physical Sciences > Physical and Theoretical Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, General Physics and Astronomy
Language:English
Date:21 October 2020
Deposited On:02 Feb 2021 12:49
Last Modified:25 Mar 2024 02:48
Publisher:American Institute of Physics
ISSN:0021-9606
OA Status:Green
Publisher DOI:https://doi.org/10.1063/5.0025787
PubMed ID:33092354
  • Content: Accepted Version