Photon correlation spectra of poly(phenylmethyl siloxane) under high pressures

We report polarized photon correlation measurements of bulk poly(phenylmethyl siloxane) (PPMS) with a molecular weight of about 2500 at different pressures from 1 to 1750 bar and temperatures between 269 and 308 K. In the Frequency range accessible by present-day digital correlators, the time correlation function can measure a slow q²-dependent diffusional process due to local concentration fluctuations and a fast α-mode structural relaxation process. The mean characteristic times of the two processes approach each other at low temperatures and high pressures, in contrast to the behavior of the α- and β-relaxation times. We should be cautious in relating the mean characteristic times for the structural relaxation process obtained by different experimental techniques, such as Brillouin scattering and photon correlation spectroscopy, because of the differnces in the probe emphasis and the extremely broad frequency distribution of such relaxation processes.