Positron annihilation response and broadband dielectric spectroscopy: salol

A phenomenological analysis of the ortho-positronium (o-Ps) annihilation from positron annihilation lifetime spectroscopy (PALS) and the dynamics from broadband dielectric spectroscopy (BDS) are reported on a small molecular glass former of intermediate H-bonding and fragility: salol. The dielectric spectra extend over a very broad frequency range of about 2 × 10(-2)-3.5 × 10(11) Hz, providing information on the α-relaxation, the secondary relaxation giving rise to the excess wing, and the shallow high-frequency minimum in the micro- to milli-meter wave range. A number of empirical correlations between the o-Ps lifetime, τ(3)(T), and the various spectral and relaxation features have been observed. Thus, the phenomenological evaluation of the τ(3)(T) dependence of the PALS response of the amorphous sample reveals three characteristic PALS temperatures: T(g)(PALS), T(b1)(L) = 1.15T(g)(PALS) and T(b2)(L) = 1.25T(g)(PALS), which are discussed in relation to similar findings for some typical small molecular vdW- and H-bonded glass formers. A slighter change of the slope at T(b1)(L) appears to be related to the transition from excess wing to the primary α-process-dominated behavior, with the secondary process dominating in the deeply supercooled liquid state below T(b1)(L). The high-temperature plateau effect in the τ (3)(T) plot occurs at T(b2)(L) and agrees with the characteristic Stickel temperature, T(B)(ST), marking a qualitative change of the primary α process, but it does not follow the relation T(b2)(L) < T(α) [τ(3)(T(b2)) < τ(α)]. Both effects at T(b1)(L) and T(b2)(L) correlate with two crossovers in the spectral shape and related non-exponentiality parameter of the structural relaxation, β (KWW). Finally, the application of the two-order parameter (TOP) model to the structural relaxation as represented by the primary α relaxation times from BDS leads to the characteristic TOP temperature, T(m)(c), close to T(b1) from PALS. Within this model the phenomenological interpretation is offered based on changes in the probability of occurrence of solid-like and liquid-like domains to explain the dynamic as well as PALS responses. In summary, all the empirical correlations support further very close connections between the PALS response and the dielectric relaxation behavior in small molecule glass formers.