The phase diagram of water from quantum simulations

Abstract

The phase diagram of water has been calculated for the TIP4PQ/2005 model, an empirical rigid non-polarisable model. The path integral Monte Carlo technique was used, permitting the incorporation of nuclear quantum effects. The coexistence lines were traced out using the Gibbs-Duhem integration method, once having calculated the free energies of the liquid and solid phases in the quantum limit, which were obtained via thermodynamic integration from the classical value by scaling the mass of the water molecule. The resulting phase diagram is qualitatively correct, being displaced to lower temperatures by 15-20K. It is found that the influence of nuclear quantum effects are correlated to the tetrahedral order parameter.

10 pages, 6 figures, 1 table

References in corpus (7)

• Competing quantum effects in the dynamics of a flexible water model
• Nuclear quantum effects in water
• Efficient stochastic thermostatting of path integral molecular dynamics
• Determination of phase diagrams via computer simulation: Methodology and applications to water, electrolytes and proteins
• Ab initio melting curve of molybdenum by the phase coexistence method
• Quantum contributions in the ice phases: the path to a new empirical model for water -- TIP4PQ/2005
• Computing the free energy of molecular solids by the Einstein molecule approach: Ices XIII and XIV, hard-dumbbells and a patchy model of proteins

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