Journal of Chemical Physics, Vol.110, No.8, 3643-3646, 1999
What causes the vibrational lifetime plateau in supercritical fluids?
Using molecular dynamics simulation, we show that the vibrational relaxation lifetime of a diatomic in a two-dimensional supercritical rare-gas fluid exhibits the same unexpected plateau behavior as was observed experimentally for W(CO)(6) in supercritical CO2 by Fayer and co-workers, and we link this behavior to average local solvent density enhancements arising from the solvent's near-critical density fluctuations.
Keywords:CRITICAL-POINT;RELAXATION;SOLUTE;SPECTROSCOPY;FLUORESCENCE;SIMULATION;CLUSTERS;MIXTURES;DENSITY;STATE