Unusual features of long-range density fluctuations in glass-forming organic liquids: a Rayleigh and Rayleigh-Brillouin light scattering study.

Abstract

A new feature of glass-forming liquids, i.e., long-range density fluctuations of the order of 100 nm, has been extensively characterized by means of static light scattering, photon correlation spectroscopy and Rayleigh-Brillouin spectroscopy in orthoterphenyl (OTP) and 1,1-di(4(')-methoxy-5(')methyl-phenyl)-cyclohexane (BMMPC). These long-range density fluctuations result in the following unusual features observed in a light scattering experiment, which are not described by the existing theories: (i) strong q-dependent isotropic excess Rayleigh intensity, (ii) additional slow component in the polarized photon correlation function, and (iii) high Landau-Placzek ratio. These unusual features are equilibrium properties of the glass-forming liquids and depend only on temperature, provided that the sample has been equilibrated long enough. The temperature-dependent equilibration times were measured for BMMPC and are about 11 orders of magnitude longer than the alpha process. It was found that the glass-forming liquid OTP may occur in two states: with and without long-range density fluctuations ("clusters"). We have characterized the two states by static and dynamic light scattering in the temperature range from T(g) to T(g)+200 K. The relaxation times of the alpha process as well as the parameters of the Brillouin line are identical in both OTP with and without clusters. The alpha process (density fluctuations) in OTP was characterized by measuring either the polarized (VV) or depolarized (VH) correlation function, which are practically identical and q-independent. This feature, which is commonly observed in glass-forming liquids, is not fully explained by the existing theories.