Abstract
The authors report picosecond absorption-recovery laser spectroscopic studies of the orientational relaxation times (tau/sub rot/) of the structurally similar probe molecules resorufin (anion) and cresyl violet (cation) in a series of binary systems comprising Me/sub 2/SO and water. While these probe molecules exhibit a hydrodynamic-like response in pure H-bonded solvents, a qualitatively different behavior is recorded in these binary systems. A distinctive curvilinear dependence of tau/sub rot/ on viscosity is observed. The introduction of dielectric friction to the theoretically calculated response of the host molecular fluid is investigated, but in contrast to results for tau/sub rot/ in H-bonded systems, this does not appear to predict the observed behavior. Attention is focused on investigating the microscopic dynamics in electrolyte solutions as an alternative approach.
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