Real-time probing of intramolecular vibrational energy redistribution and intermolecular vibrational energy transfer of selectively excited CH2I2 molecules in solution

Abstract

Competition between intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) of excited methylene iodide (CH2I2) in solution has been measured in real time. After excitation of the C-H- stretch overtone and C-H- stretch containing combination bands of CH2I2 between 1.7 and 2.4 mum an increase followed by a decrease in the transient electronic absorption at 400 nm has been monitored. The transient absorption has been attributed to vibrational energy flow from the initially excited degrees of freedom to vibrational states with larger Franck-Condon (FC) factors for the electronic transition (long wavelength wing) and energy loss due to energy transfer to the solvent. A model based upon the dependence of the electronic absorption on the internal energy <E > of CH2I2 has been used to determine the times for intramolecular vibrational energy redistribution and intermolecular energy transfer to the solvent. in the simplest version of our model the internal energy of the molecule probed by the population of the FC-active modes rises and decays exponentially on a picosecond (ps) time scale, which reflects the initial intramolecular vibrational energy redistribution and the subsequent energy transfer to the solvent. This simple approach was able to accurately describe the measured transient absorption for all solvents and excitation wavelengths. Overall time constants for IVR have been found to be on the order of 9-10 ps, almost independent of the excitation wavelength, the excited modes, and the solvent. In contrast, energy transfer to the solvent takes significantly longer. Overall time constants for VET have been determined in the range between 60 and 120 ps depending on the solvent, the excitation energy, but not on the mode which was initially excited.