The dynamics of azulene in liquids and compressed gases on ultrafast timescales

Abstract

The ultrafast dynamics of vibrationally hot ground state azulene molecules have been time resolved by picosecond transient absorption spectroscopy in a variety of solvents including hexane, chloromethanes, methanol, CClF3, Xe and Kr. A high pressure optical cell was used to liquify gases for use as solvents and change their density and temperature, independently, over the entire liquid density range. Experimental results indicate the vibrational cooling rate is strongly solvent dependent, with cooling rates of approximately 20 psec in molecular solvents and approximately 150 psec in atomic solvents. Comparison of the rates in Xe and Kr at constant 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. This latter result is quite surprising in light of earlier experiments on simpler molecular systems, such as I2 in Xe. This anomalous density effect is examined in light of Isolated Binary Collision (IBC) theory and bulk thermal transport models. Both theories accurately model all experimental results obtained with the exception of the density effort. Possible explanations for the breakdown of the IBC theory in this case are offered along with methods to improve IBC theory for application to complex three dimensional molecular systems.