The applicability of binary collision theories to complex molecules in simple liquids

The relaxation dynamics of vibrationally excited ground-state azulene molecules have been examined by picosecond transient absorption spectroscopy in a variety of different solvents including hexane, chloromethanes, methanol, CClF3, Xe, and Kr. A high pressure optical cell was used to liquify gases for use as solvents and to change their density and temperature independently over the entire liquid density range. Experimental results indicate that the vibrational cooling rate is strongly solvent dependent, with cooling rates of approximately 20 ps in molecular solvents and approximately 150 ps in atomic solvents. Comparison of the rates in Xe and Kr at constant number density demonstrates the strong effect of solvent mass on energy transfer. The effect of solvent temperature on vibrational cooling is minimal, as is the effect of solvent density. The latter result is quite surprising in light of earlier experiments on simpler molecular systems, such as I2 in Xe, and predictions of isolated binary collision theories. An explanation is offered from large scale molecular dynamics simulations of the system. In effect, azulene forms an ''ordered Xe cluster'' with xenon atoms; the xenon number density normal to the azulene molecular plane is independent of solvent density