Residual entropy of ice III from Monte Carlo simulation

摘要

We calculated the residual entropy of ice III as a function of the occupation probabilities of hydrogen positions alpha and beta assuming equal energies of all configurations. To do this, a discrete ice model with Bjerrum defect energy penalty and harmonic terms to constrain the occupation probabilities was simulated by the Metropolis Monte Carlo method for a range of temperatures and sizes followed by thermodynamic integration and extrapolation to N = infinity. Similarly as for other ices, the residual entropies are slightly higher than the mean-field (no-loop) approximation. However, the corrections caused by fluctuation of energies of ice samples calculated using molecular models of water are too large for accurate determination of the chemical potential and phase equilibria. (C) 2016 AIP Publishing LLC.