Large-scale molecular dynamics simulations (64 000 particles) are used to examine the microscopic mechanism of crystal nucleation and growth in a slightly supersaturated solution of NaCl in water at 300 K and 1 atm. Early-stage nucleation is observed, and the growth of a single crystal is followed for ∼140 ns. It is shown that the nucleation and growth process is better described by Ostwald's rule of stages than by classical nucleation theory. Crystal nucleation originates in a region where the local salt concentration exceeds that of the bulk solution. The early-stage nucleus is a loosely ordered arrangement of ions that retains a significant amount of water. The residual water is slowly removed as the crystal grows and evolves toward its stable anhydrous state.
We have carried out ab initio molecular dynamics simulations of a liquid-vapor interfacial system consisting of a mixture of water and ammonia molecules. We have made a detailed analysis of the structural and dynamical properties of the bulk and interfacial regions of the mixture. Among structural properties, we have looked at the inhomogeneous density profiles of water and ammonia molecules, hydrogen bond distributions, orientational profiles, and also vibrational frequency distributions of bulk and interfacial molecules. It is found that the interfacial molecules show preference for specific orientations so as to form water-ammonia hydrogen bonds at the interface with ammonia as the acceptor. The structure of the system is also investigated in terms of inter-atomic voids present in the system. Among the dynamical properties, we have calculated the diffusion, orientational relaxation, hydrogen bond dynamics, and vibrational spectral diffusion in bulk and interfacial regions. It is found that the diffusion and orientation relaxation of the interfacial molecules are faster than those of the bulk. However, the hydrogen bond lifetimes are longer at the interface which can be correlated with the time scales found from the decay of frequency time correlations.
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