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

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.