Vibrational energy dynamics of normal and deuterated liquid benzene

Ultrafast Raman spectroscopy with infrared (IR) excitation is used to study vibrational energy dynamics of ambient temperature liquids benzene and benzene-d(6). After IR pumping of a CH-stretch or CD-stretch parent excitation, the redistribution of vibrational energy is probed with anti-Stokes Raman. Ten benzene or 12 benzene-d(6) vibrations out of 30 total have large enough cross sections to be observed. The pathways, quantum yields, and lifetimes for energy transfer among these vibrations are quantified. Using a CCl(4) molecular thermometer, we demonstrate an ultrafast Raman calorimetry method which allows measurement of the rate that benzene vibrational energy is dissipated into the bath. On the basis of energy conservation, we then determine the time-dependent dissipation of aggregate vibrational energy from the unobserved, "invisible" vibrations. During the approximately 1 ps IR excitation process, vibrational energy is coherently redistributed to several vibrational modes ("coherently" means the rate is faster than (T(2))(-1) of the pumped transition). This energy is then further redistributed in an incoherent intramolecular vibrational relaxation process with a 6 ps T(1) time constant. The subsequent dynamics involve energy transfer processes accompanied by vibrational energy dissipation to the bath. This vibrational cooling process has a half-life of 30 ps in benzene and 20 ps in benzene-d(6), and thermalization is complete in approximately 100 ps. The observed strongly Raman-active vibrations have about the same amount of energy per mode as the invisible vibrations. The invisible vibrational energy in benzene decays somewhat faster than the observed energy. These two decay rates are about the same in benzene-d(6).