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The Kinetics Of Solvent Reorientation In Hydroxylated Solvents From The Exciting-Wavelength Dependence Of Chromophore Emission Spectra, John Milton, Robert M. Purkey, William C. Galley
The Kinetics Of Solvent Reorientation In Hydroxylated Solvents From The Exciting-Wavelength Dependence Of Chromophore Emission Spectra, John Milton, Robert M. Purkey, William C. Galley
WM Keck Science Faculty Papers
The disappearance of the exciting-wavelength dependence of the phosphorescence spectra of polar, aromatic chromophores in supercooled glycol–water mixtures is utilized to monitor the kinetics of solvent reorientation. Reorientation times in the nanosecond to second range are obtained for (3:2 v/v) glycerol–water and (1:1 v/v) ethylene glycol–water at 140–240 °K. The results suggest that the process is one involving a cluster of solvent molecules and in which the chromophore plays a relatively passive role. Steady-state data and direct measurements of phosphorescence shifts as a function of time indicate that the solvent reorientation process is nonexponential in nature. The decay function derived …