Abstract

Understanding the magnitudes and time-scales of the intermolecular interactions that occur during a chemical reaction in the liquid phase is a central problem in condensed phase studies. Assuming linear response and validity of the Fluctuation-Dissipation theorem, knowledge of the processes and related time scales by which the neat solvent molecules fluctuate and relax in an equilibrium system (that is, in the absence of the strong perturbation produced by a reacting chromophore) is directly related to knowing the solvent modes available for acceptance of excess energy during the course of a reaction.¹ Such equilibrium spectra may be obtained from optical Kerr effect studies² or far-infrared (i. e. terahertz) dipolar absorption measurements.³

© 1996 Optical Society of America