Density anomaly of water at negative pressures from first principles

A Singraber and T Morawietz and J Behler and C Dellago, JOURNAL OF PHYSICS-CONDENSED MATTER, 30, 254005 (2018).

DOI: 10.1088/1361-648X/aac4f4

Using molecular dynamics simulations based on ab initio trained high- dimensional neural network potentials, we study the equation of state of liquid water at negative pressures. From density isobars computed for various pressures down to p = -230 MPa we determine the line of density maxima for two potentials based on the BLYP and the RPBE functionals, respectively. In both cases, dispersion corrections are included to account for non-local long-range correlations that give rise to van der Waals forces. We have followed the density maximum down to negative pressures close to the spinodal instability. For both functionals, the temperature of maximum density increases with decreasing pressure under moderate stretching, but changes slope at p approximate to -200 MPa and p approximate to -20 MPa for BLYP and RPBE, respectively. Our calculations confirm qualitatively the retracing shape of the line of density maxima found for empirical water models, indicating that the spinodal line maintains a positive slope even at strongly negative pressures.

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