Two-dimensional measurements of the solvent structural relaxation dynamics in dipolar solvationw

Resonant-pump polarizability response spectroscopy (RP-PORS) is based on an optical heterodyne detected transient grating (OHD-TG) method with an additional resonant pump pulse. In RP-PORS, the resonant pump pulse excites the solute–solvent system and the subsequent relaxation of the solute–solvent system is monitored by the OHD-TG spectroscopy. RP-PORS is shown to be an excellent experimental tool to directly measure the solvent responses in solvation. In the present work, we extended our previous RP-PORS (Park et al., Phys. Chem. Chem. Phys., 2011, 13, 214–223) to measure time-dependent transient solvation polarizability (TSP) spectra with Coumarin153 (C153) in acetonitrile. The time-dependent TSP spectra showed how the different solvent intermolecular modes were involved in different stages of the solvation process. Most importantly, the inertial and diffusive components of the solvent intermolecular modes in solvation were found to be spectrally and temporally well-separated. In a dipolar solvation of C153, high-frequency inertial solvent modes were found to be driven instantaneously and decay on a subpicosecond timescale while low-frequency diffusive solvent modes were induced slowly and decayed on a picosecond timescale. Our present result is the first experimental manifestation of frequency-dependent solvent intermolecular response in a dipolar solvation.