Free volume in the smectic-E phase of 4-hexyl-4' isothiocyanatobiphenyl studied by positron annihilation spectroscopy.

Positron annihilation lifetime spectroscopy has been used to study 4-hexyl-4'-isothiocyanatobiphenyl. Changes of the orthopositronium lifetime parameters with temperature have been observed for the supercooled smectic-E phase. The measurements confirm that positronium is created and annihilates in a layer of a lower electron density containing alkyl chains of molecules. The two-state bond-lattice model of glass transition explains the thermal activation of the centers where orthopositronium is created and annihilates when the glass of the smectic-E phase softens. However, the subsequent cold crystallization of the softened regions also influences the orthopositronium lifetime and intensity, which complicates the picture seen by positrons. The measurements during isothermal crystallization suggest that it progresses in two stages. The first stage can be described by the Avrami equation with the Avrami exponent close to unity, which indicates low-dimensional crystallization. Similarly to liquid n alkanes, the application of pressure is equivalent to temperature lowering with the similar equivalence relationship between pressure and temperature, which seems to confirm the structure of the smectic-E phase with sublayers containing alkyl chains in a molten state. The dependence of the orthopositronium lifetime on pressure for the smectic-E phase may be described by the bubble model where the positronium bubble is approximated with a finite square potential well with the depth of U = 1.45 eV.