Role of the density in the crossover region of o-terphenyl and poly(vinyl acetate).

The coupling between the reorientation of molecular probes and the density in one low-molar mass glass former [ o -terphenyl (OTP)] and one polymer [poly(vinyl acetate) (PVAc)] is studied in the Goldstein's crossover region where the structural (alpha) and the secondary (beta) relaxations bifurcate. The coupling is found to be strong in OTP and virtually absent in PVAc. The probes sense both the alpha and beta relaxations, and locate their splitting accurately. It is concluded that the density affects the relaxation occurring in the crossover region of OTP but not of PVAc at subnanometer length scales. The findings are compared with recent assessments of the role of the molecular packing close and above the glass transition temperature T(g).