Temperature dependence of the free volume from positron lifetime experiments and its relation to structural dynamics: phenylphthalein-dimethylether.

Positron annihilation lifetime spectroscopy (PALS) was used to study the microstructure of the free volume in the temperature range between 103 K and 393 K in phenylphthalein-dimethylether (PDE), a low-molecular-weight glass former. Using the routine LIFETIME9.0, the ortho-positronium (o-Ps) lifetime distribution was analyzed, and from this, the volume distribution gn(vh) of subnanometer-size holes was calculated. From a comparison of PALS and specific volume data, the number density and the volume fraction of holes were estimated. These free-volume data, as a function of temperature, were used to test the validity of the Cohen-Turnbull (CT) free-volume theory. It was found that the structural relaxation from dielectric spectroscopy can be described by the CT theory after introducing a corrected free volume (Vf-DeltaV), where DeltaV=0.014 cm3/g. The extended free-volume theory of Cohen and Grest can be fitted to the dielectric-relaxation and free-volume data, but the parameters of both fits are not consistent. PDE shows some peculiar features. The "knee" in the o -Ps lifetime expansion and crossover in temperature dependence of the frequency of the primary dielectric relaxation process occur at different temperatures. In addition, the change in the Vogel-Fulcher-Tammann parameters at TB/Tg=1.1 has no observable effect on the mean free volume vh (or Vf). The size of the smallest representative freely fluctuating subsystem, VSV estimated from the standard deviation sigmah of gn(vh), decreases from 4.1 nm3 to 2.6 nm3 when the temperature increases from T/Tg=1.0 to 1.15. Correspondingly, the length of dynamic heterogeneity, xi=VVS1/3, decreases from 1.6 nm to 1.4 nm. It is concluded that at T/Tg approximately 1.10=TB/Tg the system transforms from a heterogeneous to a homogeneous (true) liquid.