Header

UZH-Logo

Maintenance Infos

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.

Statistics

Citations

Dimensions.ai Metrics
10 citations in Web of Science®
10 citations in Scopus®
4 citations in Microsoft Academic
Google Scholar™

Altmetrics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 University Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2017
Deposited On:09 Feb 2018 08:04
Last Modified:18 Apr 2018 11:49
Publisher:American Chemical Society (ACS)
ISSN:1948-7185
Funders:SNF (grant number CRSII2_160801)
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acs.jpclett.7b01034
Project Information:
  • : FunderSNSF
  • : Grant ID
  • : Project TitleSNF (grant number CRSII2_160801)

Download

Full text not available from this repository.
View at publisher

Get full-text in a library