The Free Volume of Condensed Phases Confined in a Nanopore as Seen by Computer Simulations and Compared to PALS

In this contribution the free volume of glycerol phase confined in a nanopore in a wide temperature range is computed. The computed free volume is compared to the previously computed values in the glycerol bulk. The mean cavity volumes are also discussed with the experimental measurements by positronium annihilation lifetime spectroscopy. The computer simulations show that in the case of the confined glycerol phase the mean cavity volumes are larger than in the simulated bulk, and also the temperature dependence has a different qualitative behavior; the computed data are in agreement with experimental measurements performed for glycerol in a pore of comparable size with diameter 6 nm. The simulations also indicate that an aspect of filling a pore is important for experimentalists. In the case of a perfectly sealed pore the cavity volume is observed to rise with decreasing temperature

Insights into positron annihilation lifetime spectroscopy by molecular dynamics simulations

The relationship between free-volume properties measured from positron annihilation lifetime spectroscopy (PALS) and calculated from molecular dynamics simulations has been investigated for glassy and liquid glycerol in the temperature range 150–400 K. A virtual probing procedure has been developed to retrieve information on the basic free-volume properties of the simulated microstructures, i.e. mean cavity volume and free-volume cavity fractions. Our data leads us to infer on the occurrence of experimentally non-detectable small cavities with mean equivalent radius of 1.8–1.9 Å between 250 and 275 K. The size of these limiting cavities is found to be temperature dependent, being smaller at low temperatures. At high temperatures, above a characteristic PALS temperature $T_{b2}^{L}$, the formation of very large cavities is predicted. This finding suggests that, when the dimension of the holes in the system exceeds a given value, the PALS measurements become unable to catch the complete structural information and phenomena of dynamical origin enter into play in the PALS signal decay. The calculated number of cavities is found to be almost independent on the temperature from the glassy up to the liquid phase, thus furnishing a certain support to theoretical models proposed to evaluate the free-volume cavity fractions