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A glass is a non-equilibrium thermodynamic state whose physical properties depend on time. Glass formation from the melt, as well as the inverse process of liquid structural recovery from the glass are non-equilibrium processes. A positive amount of entropy is produced during such irreversible processes. In this paper, we address the issue of the determination of entropy production during glass transition. Firstly, we theoretically determine the entropy production by means of the statistical model of a two-level system coupled to a master equation driving the time dependency of the occupancy probability of each state. Thermodynamic cycles of the type liquid-glass-liquid are considered in order to test the validity of the Clausius theorem. Secondly, we determine experimentally the production of entropy from differential scanning calorimetry experiments on the PolyVinylAcetate glass-former. Aging experiments are also considered. From the data treatments proposed here, we are able to determine the rate of production of entropy in each part of the experiments. Although being on the order of few % or less of the configurational entropy involved in the glass formation, the positive production of entropy is clearly determined. For all the thermodynamic cycles considered in these calorimetric experiments, the Clausius theorem is fulfilled.

The influences of water molecules surrounding biological molecules during irradiation with heavy particles (atoms,ions) are currently a major subject in radiation science on a molecular level. In order to elucidate the underlying complex reaction mechanisms we have initiated a joint experimental and theoretical investigation with the aim to make direct comparisons between experimental and theoretical results. As a first step, studies of collisions of a water molecule with a neutral projectile (C atom) at high velocities (> 0.1 a.u.), and with a charged projectile (proton) at low velocities (< 0.1 a.u.) have been studied within the microscopic framework. In particular, time-dependent density functional theory (TDDFT) was applied to the valence electrons and coupled non-adiabatically to Molecular dynamics (MD) for ionic cores. Complementary experimental developments have been carried out to study projectile interactions with accelerated (< 10 keV) and mass-selected cluster ions. The first size distributions of protonated water cluster ions H+(H_2O)_n (n=2-39) produced using this new apparatus are presented., Comment: 8 pages, 4 figures, subm. to International Journal of Mass Spectrometry

A complete set of cross sections is reported for the ionization of water molecules by neutral atomic hydrogen impact at velocities of the order of the Bragg peak. The measured relative cross sections are normalized by comparison with proton impact results for the same target conditions and previous absolute data. Event by event coincidence analysis of the product ions and the projectile enables partial cross sections for target ionization and target plus projectile ionization to be determined, as well as total cross sections for electron loss reactions., Comment: To be published in Chemical Physics Letters

Absolute dissociation cross sections are reported for Hn+ clusters of varied mass (n = 3, 5, ..., 35) following collisions with He atoms at 60 keV / amu. Initial results have been published in a previous brief report for a smaller range of cluster sizes [Ouaskit et al., Phys. Rev. A 49, 1484 (1994)]. The present extended study includes further experimental results, reducing the statistical errors associated with the absolute cross sections. The previously suggested quasi-linear dependence of the Hn+ dissociation cross sections upon n is developed with reference to expected series of geometrical shells of H2 molecules surrounding an H3+ core. Recent calculations identify n = 9 as corresponding to the first closed H2 shell [e.g. Stich et al., J. Chem. Phys. 107, 9482 (1997)]. Recurrence of the distinct characteristics observed in the dissociation cross section dependence upon cluster size around n = 9 provides the basis for the presently proposed subsequent closed shells at n = 15, 21, 27, and 33, in agreement with the calculations of Nagashima et al. [J. Phys. Chem. 96, 4294 (1992)]., Comment: To be published in Physical Review A