Solvation dynamics in nonassociated polar solvents

Abstract

Ultrafast solvation dynamics in three nonassociated polar solvents, namely, acetonitrile, dimethyl sulfoxide, and acetone, have been studied by using the molecular hydrodynamic theory. For solvation in acetonitrile, the solvent memory function required for this study has been obtained from recent dielectric relaxation measurements of Venabales and Schuttenmaer; earlier theoretical studies used only the Kerr relaxation data. As the latter provides only an indirect information regarding the polar dynamical response of the dipolar liquid, it fails to provide a fully quantitative description of the solvation time correlation function, S(t). The present study with full dielectric data, on the other hand, gives excellent agreement with the experimental results. The theory shows that the ultrafast part of the solvation dynamics originates almost entirely from the high-frequency component of dielectric relaxation (with time constant 0.177 ps), although the latter represents only a small part of the latter. For DMSO and acetone, however, the present theory predicts a decay slower than the experimental observation. It is proposed that for these two solvents specific chromophore−solvent interactions might be responsible for the large discrepancy. On the basis of the theory, two experimental studies have also been proposed.