Empirical Analysis of Optical Kerr Effect Spectra: A Case for Constraint.

Abstract

Ultrafast optical Kerr effect (OKE) spectroscopy is a widely used method for studying the depolarized, Raman-active intermolecular dynamics of liquids. Through appropriate manipulation of OKE data, it is possible to determine the reduced spectral density (RSD), which is the Bose-Einstein-corrected, low-frequency Raman spectrum with the contribution of diffusive reorientation removed. OKE RSDs for van der Waals liquids can often be fit well to an empirical function that is the sum of a Bucaro-Litovitz function and an antisymmetrized Gaussian (AG). Although these functions are not directly representative of specific intermolecular dynamics, the AG fit parameters can provide useful insights into the microscopic properties of liquids. Here we show that fits using the AG function are typically not well-determined, and that equally good results can be obtained with a wide range of fitting parameters. We propose the use of a physically motivated constraint on the amplitude of the AG function, and demonstrate that this constraint leads to more intuitive trends in the fit parameters for temperature-dependent RSDs in 1,3,5-trifluorobenzene and hexafluorobenzene.