Abstract

Current theoretical studies by a number of workers have focussed attention on the importance of solvation dynamics in determining the rates of reactions in solution¹. This is especially true of reactions involving substantial charge redistribution in the reaction coordinate in polar solvents, where solvation energies may be quite large. The first step in testing these ideas is to obtain direct, microscopic measures of the kinetics of dipolar solvation. Experimentally, such information is available by monitoring the temporal evolution of the electronic spectrum of a probe solute after instantaneously changing its charge or dipole moment. Spectral shifts as a function of time directly monitor the course of solvation as the system reequilibrates to the new solute charge distribution.

© 1986 Optical Society of America