Monte Carlo (MC) simulations were performed for hard spheres (with diameter sigma and mass m) placed between well-separated upper and lower hard walls. A periodic boundary condition was imposed in the horizontal direction. The system was exposed to the gravitational field with the acceleration due to gravity g. After preparing a melt as the initial state, g was increased stepwise up to mgsigma/k(B)T(identical with g(*))=1.5 or 2.0 with an increment Deltag(*) = 0.1; k(B)T is the temperature multiplied by Boltzmann's constant. We maintained g(*) at each value for 2.0 x 10(5) MC cycles. The transition of the system into a metastable state such as a polycrystalline state due to trapping phenomena was successfully avoided. A monotonic increase and subsequent saturation were observed for the development of the crystalline region formed at the bottom of the system. The development of this region accompanied a shrinkage of the defective (or less ordered) crystalline region that was formed between the bottom region and the fluid phase. As the development of the bottom region almost saturated, the defective region grew upward again.

Disappearance of a stacking fault in the hard-sphere crystal under gravity, such as reported by Zhu et al. [Nature 387, 883 (1997)], has successfully been demonstrated by Monte Carlo simulations. We previously found that a less ordered (or defective) crystal formed above a bottom ordered crystal under stepwise controlled gravity [Mori et al. J. Chem. Phys. 124, 174507 (2006)]. A defect in the upper defective region has been identified with a stacking fault for the (001) growth. We have looked at the shrinking of a stacking fault mediated by the motion of the Shockley partial dislocation; the Shockley partial dislocation terminating the lower end of the stacking fault glides. In addition, the presence of crystal strain, which cooperates with gravity to reduce stacking faults, has been observed.

Solubility of glucose isomerase (from Streptomyces rubiginosus) crystals was measured in situ at 0.1 and 100 MPa. An equilibrium temperature of the crystal with the solution of a given concentration was measured using a two-beam interferometer. The solubility of the crystal decreased to about one-ninth with increasing pressure from 0.1 to 100 MPa at 30 °C. This means that the supersaturation, σ () ln C/C e , C ) protein concentration, C e ) solubility), increases significantly with increasing pressure at the same temperature. This strongly suggests that the substantial acceleration of the crystallization of glucose isomerase with increasing pressure reported by Visuri et al. is due to the significant decrease in the solubility. The enthalpy and entropy of the dissolution were estimated from the van't Hoff plots. The volume change accompanying the dissolution took a large positive value as ∆V ) 54 ( 31 cm 3 mol -1 at 30 °C.

Monte Carlo simulations were performed for hard spheres (HSs) under gravity. The gravity was increased stepwise. HSs were placed between the bottom and the top hard walls. For g*R0.9, we observed that a 'sediment' was comprised of two crystalline and one fluid regions. Here, g* is defined by g*Zmgs/k B T with m being the mass of a particle, s the HS diameter, g the acceleration due to gravity, and k B T the temperature multiplied by Boltzmann's constant. The bottom crystal was less defective or well-ordered and the crystal lay between the bottom one and the fluid phase was defective or less-ordered. In this paper, we investigate the structure of the crystals. Despite no apparent defects, the crystal has highly been distorted. That is, the fcc lattice has been contracted in the vertical direction more than in the horizontal direction. The crystal-fluid coexistence condition for the bulk HS system does, in principle, not hold for the present systems at the crystal-fluid interface. In addition, though the fine scale density profile exhibits a discontinuity apparently across the crystal-crystal interface, the interlayer separation increases linearly with the height. q