Journal of Chemical Physics, Vol.115, No.10, 4689-4695, 2001
Temperature and density dependent solute vibrational relaxation in supercritical fluoroform
Temperature- and density-dependent vibrational relaxation data for the upsilon (6) asymmetric stretch of W(CO)(6) in supercritical fluoroform (trifluoromethane, CHF3) are presented and compared to a recent theory of solute vibrational relaxation. The theory, which uses thermodynamic and hydrodynamic conditions of the solvent as input parameters, shows very good agreement in reproducing the temperature- and density-dependent trends of the experimental data with a minimum of adjustable parameters. Once a small number of parameters are fixed by fitting the functional form of the density dependence, there are no adjustable parameters in the calculations of the temperature dependence.