Positron annihilation lifetime response and relaxation dynamics in glycerol

Positron annihilation lifetime spectroscopy (PALS) data on glycerol are related to the results of broadband dielectric studies from the literature. Specifically, the temperature variation of the ortho-positronium (o-Ps) lifetime, τ3, and of the relative intensity, I3, from 100 K up to 300 K have been compared with the spectral features of the α and β relaxation from the decomposed dielectric loss spectra. First, it is found that in the τ3 vs. temperature plot, in addition to the universal characteristic PALS temperatures: T g PALS and T b 2 L = 1.53 T g PALS where large discontinuities in slope are observed and which are associated with the glass–liquid transition and the onset of a quasi-plateau level, respectively, a discontinuity in the slope occurs at T b 1 L = 1.28 T g PALS . Further, it is found that τ3 at T b 1 L is approximately the same as the mean secondary β relaxation time, τ 3 ( T b 1 L ) ≈ τ β ( T b 1 L ) . Next, it is suggested that the decrease in the I3 vs. T plot as temperature increases above T g PALS can be related to the β and α relaxations qualitatively. These findings are consistent with the notion that free volume redistribution in liquid glycerol is due to the local β process as well as the high-frequency part of cooperative α process causing a partial elimination of smaller holes from the PALS spectrum as temperature increases. An alternative or perhaps additional explanation is that as temperature increases, some of the small, detectable holes break up into holes too small for the PALS measurement.