Ultrafast Vibrational Energy Transfer in Catalytic Monolayers at Solid-Liquid Interfaces.

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.