Theoretical Study of Internal Vibrational Relaxation and Energy Transport in Polyatomic Molecules

We attempted to theoretically characterize internal vibrational relaxation and energy relaxation pathways due to anharmonicity in polyatomic molecules. Energy transport dynamics have been modeled based on a generalization of Marcus electron transfer theory. Modifications have been made to our previously developed theory in order to improve the description of internal vibrational dynamics. We applied our method to several molecules studied experimentally by relaxation-assisted two-dimensional infrared spectroscopy (RA 2DIR). The theoretical predictions were found to be consistent with the majority of the experimental data.