Structure and dynamics of water plastic crystals from computer simulations.

Water has a rich phase diagram with several crystals, as confirmed by experiments. High-pressure and high-temperature water is of interest for Earth's mantle and exoplanetary investigations. It is in this region of the phase diagram of water that new plastic crystal phases of water have been revealed via computer simulations by both classical forcefields and ab initio calculations. However, these plastic phases still remain elusive in experiments. Here, we present a complete characterization of the structure, dynamics, and thermodynamics of the computational plastic crystal phases of water using molecular dynamics and the two-phase thermodynamic method and uncover the interplay between them. The relaxation times of different reorientational correlation functions are obtained for the hypothetical body-centered-cubic and face-centered-cubic plastic crystal phases of water at T = 440 K and P = 8 GPa. Results are compared to a high pressure liquid and ice VII phases to improve the understanding of the plastic crystal phases. Entropy results indicate that the fcc crystal is more stable compared to the bcc structure under the studied conditions.

Relaxation Dynamics vs Crystallization Kinetics in the Amorphous State: The Case of Stiripentol.

With the aim of finding a correlation between the crystallization kinetics and the molecular dynamics of a substance that would allow prediction of its crystallization time as a function of temperature for a given α relaxation time, we have studied stiripentol, an anticonvulsant drug. Stiripentol has been characterized in its supercooled liquid, amorphous (glass), and crystalline states by the concurrent use of broadband dielectric spectroscopy (BDS), differential scanning calorimetry, X-ray diffraction, and optical microscopy. BDS was employed to study both the dipolar molecular dynamics and the kinetics of crystallization from the melt. Three different molecular relaxation dynamics were identified: an α relaxation corresponding to the collective reorientation of the molecules and associated with the glass transition (Tg = 246.2 ± 0.5 K), a Johari Goldstein ß relaxation that can be associated with the single-molecule precursor of the α process, and a γ relaxation arising from intramolecular motions. Isothermal crystallization of Stiripentol was studied by means of BDS well above the glass transition (between 273 and 293 K), and it was observed under optical microscope at ambient conditions. Stiripentol did not exhibit any sign of polymorphism at ambient pressure, and it recrystallized from the melt into its stable crystalline form. The crystallization kinetics did not obey the Avrami law. Stiripentol displayed a very low nucleation rate, and drops of liquid stiripentol were observed to crystallize completely from a single nucleus before the appearance of new nuclei, so that the crystallite grew according to the morphology of the liquid domains, a fact that might explain the lack of validity of the Avrami law. Possible correlations between the crystallization kinetics and the molecular dynamics have been analyzed, finding that the crystallization time has a sublinear dependence on the cooperative relaxation time, as is the case in other substances reported in the scientific literature. This could suggest a general correlation of these parameters, at least at temperatures above Tg. The low nucleation rate is an interesting feature in the quest of possible mechanisms that allow enhancing the physical stability of amorphous drugs.

Genuine antiplasticizing effect of water on a glass-former drug.

Water is the most important plasticizer of biological and organic hydrophilic materials, which generally exhibit enhanced mechanical softness and molecular mobility upon hydration. The enhancement of the molecular dynamics upon mixing with water, which in glass-forming systems implies a lower glass transition temperature (T g ), is considered a universal result of hydration. In fact, even in the cases where hydration or humidification of an organic glass-forming sample result in stiffer mechanical properties, the molecular mobility of the sample almost always increases with increasing water content, and its T g decreases correspondingly. Here, we present an experimental report of a genuine antiplasticizing effect of water on the molecular dynamics of a small-molecule glass former. In detail, we show that addition of water to prilocaine, an active pharmaceutical ingredient, has the same effect as that of an applied pressure, namely, a decrease in mobility and an increase of T g . We assign the antiplasticizing effect to the formation of prilocaine-H 2 O dimers or complexes with enhanced hydrogen bonding interactions.

Disentangling the secondary relaxations in the orientationally disordered mixed crystals: cycloheptanol + cyclooctanol two-component system.

The dynamics of the pure compounds and mixed crystals formed between cycloheptanol (cC7-ol) and cyclooctanol (cC8-ol) has been studied by means of broadband dielectric spectroscopy at temperatures near and above the orientational glass transition temperature. Both compounds are known to display at least one orientationally disordered (OD) phase of simple cubic symmetry, and within this phase, a continuous formation of mixed crystals was demonstrated in the past (Rute, M. A. et al. J. Phys. Chem. B 2003, 107, 5914). The dielectric loss spectra of cC7-ol and cC8-ol show, in addition to the well-pronounced alpha-relaxation peaks with a continuous temperature shift (characteristic of the freezing of the molecular dynamics), secondary relaxations (beta and gamma for cC8-ol and gamma for cC7-ol) which are intramolecular in nature. The dynamics of several OD mixed crystals was recently studied (Singh, L. P.; Murthy, S. S. N. J. Phys. Chem. B 2008, 112, 2606), and surprisingly enough one of the secondary relaxations was not evidenced. We show here by means of a careful set of measurements for several mixed crystals and of a detailed analysis procedure the existence of the secondary relaxations for the mixed crystals. The results, moreover, doubtless reinforce the physical origin of each of the secondary relaxations.

From the two-component system CBrCl3+CBr4 to the high-pressure properties of CBr4.

The experimental phase diagram of the CBrCl3+CBr4 system has been determined by means of X-ray powder diffraction and thermal analysis techniques from 200 K to the liquid state. Before melting, the two components have the same orientationally disordered (OD) face-centered cubic phase, and solid-liquid equilibrium is explained by simple isomorphism. The application of multiple crossed isopolymorphism formalism to the low-temperature solid-solid equilibria has enabled the inference of an OD rhombohedral metastable (at normal pressure) phase for CBr4. Experimental determination of the pressure-volume-temperature and construction of the pressure-temperature phase diagrams for CBr4 reveal the existence of a high-pressure phase, the rhombohedral symmetry of which is inferred by means of the thermodynamic assessment of the experimental phase diagram and demonstrated by means of high-pressure neutron diffraction measurements. The procedure used in this work confirms the connection between the appearance of metastable phases at normal pressure and their existence at high-pressure.

Multiple crossed isopolymorphism: two-component systems CCl4 +CBr2Cl2 and CBrCl3 + CBr2Cl2; inference of a metastable rhombohedral phase of CBr2Cl2.

The phases diagrams of the two-component systems CCl4 +CBr2Cl2 and CBrCl3 + CBr2Cl2 have been determined by means of X-ray powder diffraction and thermal analysis techniques from the low-temperature ordered phase to the liquid state. The isomorphism relationship between the stable orientationally disordered (OD) face-centered cubic (FCC) phases of CBrCl3 and CBr2Cl2 and the metastable OD FCC phase (monotropic behavior with respect to the OD rhombohedral stable phase) of CCl4 has been put into evidence throughout the continuous evolution of the lattice parameters and the existence of the two-phase equilibrium [FCC + L] for the whole range of composition in both two-component systems. This equilibrium interferes, for the CCl4 +CBr2Cl2 system, with a rhombohedral (R) plus liquid ([R + L]) equilibrium giving rise to a peritectic invariant. In addition, whatever the system, [R + FCC] equilibrium also interferes with the low-temperature equilibria between the low-temperature monoclinic (C2/c) phase and the OD R and FCC phases. In regards to the low-temperature monoclinic phases, isomorphism is evidenced, and by means of Rietveld profile refinement, any ordering of the molecules by varying the fractional occupancy of the halogen sites has been detected. The thermodynamic assessment, conducted by means of the concept of crossed isopolymorphism, coherently reproduces all the involved equilibria and provides a coherent set of data for the thermodynamic properties of nonexperimentally available phase transitions of pure compound CBr2Cl2 which enables us to obtain the topological properties of its pressure-temperature phase diagram and to infer the existence of a high-pressure R phase for such a compound.