Molecular Photothermal Effects on Time-Resolved IR Spectroscopy: Solute-Solvent Intermolecular Energy Transfer.

Time-resolved IR pump-probe (IR-PP) and two-dimensional IR (2D-IR) spectroscopy are valuable tools for studying ultrafast chemical and biological processes in solutions. However, the corresponding signals at long times are obscured by the molecular photothermal effects resulting from the heat dissipation of vibrationally photoexcited molecules to the surroundings. Recently, a phenomenology model was used to describe molecular photothermal effects on IR-PP signals and the diagonal and cross-peaks of 2D-IR spectra at long pump-probe delay times. Here, we consider the thermal diffusion equation with a time-dependent heat source term to describe the solute-solvent energy transfer process. An approximate solution to the nonhomogeneous differential equation shows that the molecular photothermal effect is determined by the mean intermolecular distance between IR-absorbing molecules. We show that the time profile of heat dissipation from a vibrationally excited molecule to the surroundings, which provides information about the mechanisms involved in the solute-solvent intermolecular energy transfer process in solutions, can be directly measured by analyzing the molecular photothermal IR-PP and 2D-IR signals. We anticipate that the present work can be used to interpret local heating-induced time-resolved IR spectroscopic signals and understand the rate of and the mechanisms involved in the conversion from high-frequency molecular vibrational energy to solvent kinetic energy in condensed phases.