Abstract

The decay of vibrational coherence is important because it affects the earliest stages of chemical reactions,¹-⁴ because it limits efforts at coherent control of reactions, and most generally, because it probes the solvent forces acting on the nuclear coordinates of chemical systems. A critical question in this area is the relative importance of attractive and repulsive solvent forces.⁵ Each type of force is expected to have distinctly different properties, most especially different timescales. Raman spectroscopy of high-frequency vibrations and more recently time-resolved measurements of low-frequency vibrational motion⁶s can measure the decay times of vibrational coherence. However, these techniques are relatively insensitive to the timescale of the forces driving the coherence decay.

© 1994 Optical Society of America