Depolarized light scattering versus optical Kerr effect spectroscopy of supercooled liquids: Comparative analysis

Abstract

Recently, heterodyne-detected optical Kerr effect (HD-OKE) spectroscopy was used to study dynamics of supercooled molecular liquids. The studies revealed an apparently new physical phenomenon that had not been reported before from the related depolarized light scattering (DLS), namely, an intermediate power law (nearly logarithmic decay) of the response functions [H. Cang et al., J. Chem. Phys. 118, 2800 (2003)]. Conceptually, HD-OKE and DLS data reflect optical anisotropy fluctuations mainly due to molecular reorientation dynamics in time and frequency domains, respectively. The above-mentioned effects are revealed in the mesoscopic range less, similar1 GHz ( greater, similar100 ps), where no direct comparison of the techniques was reported. In this Communication, we attempt such a comparison of exemplifying HD-OKE literature data of the glass-forming salol (phenyl salicylate), benzophenone, and liquid-crystal forming 4-cyano-4(')-pentylbiphenyl with DLS data of the same systems that we measured down to ca. 200 MHz by a combined tandem Fabry-Perot interferometer plus tandem-grating-monochromator technique. Generally, we find a satisfactory agreement, albeit in some cases with subtle differences at frequencies greater, similar10 GHz. We conclude that, in the mesoscopic dynamic range, HD-OKE and DLS studies provide consistent and comparable information, and therefore their conclusions must agree. We argue that the intermediate power law of HD-OKE is in essence a manifestation of the excess wing of the corresponding frequency-domain data, known long since from broadband dielectric spectroscopy and anticipated from DLS studies of supercooled liquids.