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Ultrafast Vibrational Energy Transfer in Catalytic Monolayers at Solid–Liquid Interfaces


Kraack, Jan Philip; Frei, Angelo; Alberto, Roger; Hamm, Peter (2017). Ultrafast Vibrational Energy Transfer in Catalytic Monolayers at Solid–Liquid Interfaces. Journal of Physical Chemistry Letters, 8(11):2489-2495.

Abstract

We investigate the ultrafast vibrational dynamics of monolayers from adsorbed rhenium–carbonyl CO2-reduction catalysts on a semiconductor surface (indium–tin-oxide (ITO)) with ultrafast two-dimensional attenuated total reflection infrared (2D ATR IR) spectroscopy. The complexes are partially equipped with isotope-labeled (13C) carbonyl ligands to generate two spectroscopically distinguishable forms of the molecules. Ultrafast vibrational energy transfer between the molecules is observed via the temporal evolution of cross-peaks between their symmetric carbonyl stretching vibrations. These contributions appear with time constant of 70 and 90 ps for downhill and uphill energy transfer, respectively. The energy transfer is thus markedly slower than any of the other intramolecular dynamics. From the transfer rate, an intermolecular distance of ∼4–5 Å can be estimated, close to the van der Waals distance of the molecular head groups. The present paper presents an important cornerstone for a better understanding of intermolecular coupling mechanisms of molecules on surfaces and explains the absence of similar features in earlier studies.

Abstract

We investigate the ultrafast vibrational dynamics of monolayers from adsorbed rhenium–carbonyl CO2-reduction catalysts on a semiconductor surface (indium–tin-oxide (ITO)) with ultrafast two-dimensional attenuated total reflection infrared (2D ATR IR) spectroscopy. The complexes are partially equipped with isotope-labeled (13C) carbonyl ligands to generate two spectroscopically distinguishable forms of the molecules. Ultrafast vibrational energy transfer between the molecules is observed via the temporal evolution of cross-peaks between their symmetric carbonyl stretching vibrations. These contributions appear with time constant of 70 and 90 ps for downhill and uphill energy transfer, respectively. The energy transfer is thus markedly slower than any of the other intramolecular dynamics. From the transfer rate, an intermolecular distance of ∼4–5 Å can be estimated, close to the van der Waals distance of the molecular head groups. The present paper presents an important cornerstone for a better understanding of intermolecular coupling mechanisms of molecules on surfaces and explains the absence of similar features in earlier studies.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Materials Science
Physical Sciences > Physical and Theoretical Chemistry
Language:English
Date:22 May 2017
Deposited On:09 Feb 2018 08:04
Last Modified:28 Jul 2020 13:11
Publisher:American Chemical Society (ACS)
ISSN:1948-7185
Funders:SNF (grant number CRSII2_160801)
Additional Information:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpclett.7b01034.
OA Status:Green
Publisher DOI:https://doi.org/10.1021/acs.jpclett.7b01034
Project Information:
  • : FunderSNSF
  • : Grant ID
  • : Project TitleSNF (grant number CRSII2_160801)

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