Plasmonic Substrates Do Not Promote Vibrational Energy Transfer at Solid-Liquid Interfaces.

Intermolecular vibrational energy transfer in monolayers of isotopically mixed rhenium carbonyl complexes at solid-liquid interfaces is investigated with the help of ultrafast 2D Attenuated Total Reflectance Infrared (2D ATR IR) spectroscopy in dependence of plasmonic surface enhancement effects. Dielectric and plasmonic materials are used to demonstrate that plasmonic effects have no impact on the vibrational energy transfer rate in a regime of moderate IR surface enhancement (enhancement factors up to ca. 30). This result can be explained with the common image-dipole picture. The vibrational energy transfer rate thus can be used as a direct observable to determine intermolecular distances on surfaces, regardless of their plasmonic properties.