NOESY-Like 2D-IR Spectroscopy Reveals Non-Gaussian Dynamics.

We have identified an unexpected signature of non-Gaussian dynamics in a conventional 2D IR measurement on a system with rapid intermolecular vibrational energy transfer. In a ternary mixture of the CO reduction photocatalyst, ReCl(bpy)(CO), NaSCN, and THF solvent, preferential association between the metal carbonyl catalyst and the NaSCN ion pairs facilitates intermolecular energy transfer on a few picoseconds time scale. Monitoring the cross peak between the highest frequency metal carbonyl band and the CN bands of NaSCN contact ion pairs, we find a striking time evolution of the cross-peak position on the detection axis. This frequency shift, which is due to spectral diffusion following intermolecular energy transfer, occurs with a time scale that is distinct from either the donor or acceptor spectral diffusion measured simultaneously. We argue that the energy transfer, a second-order Förster process, effectively increases the dimensionality of the 2D-IR spectroscopy and thus enables sensitivity to non-Gaussian dynamics.