An analysis of fluctuations in supercooled TIP4P/2005 water

Abstract

Large-scale, long-time molecular dynamics simulations are used to investigate fluctuations in the TIP4P/2005 water model in the supercooled region (240-190 K). Particular attention is focused in the vicinity of a previously reported liquid-liquid critical point [J. L. F. Abascal and C. Vega, J. Chem. Phys. 133, 234502 (2010)]. Water is viewed as an equimolar binary mixture with "species" defined based on a local tetrahedral order parameter. A Bhatia-Thornton fluctuation analysis is used to show that species concentration fluctuations couple to density fluctuations and completely account for the anomalous increase in the structure factor at small wave number observed under supercooled conditions. Although we find that both concentration and density fluctuations increase with decreasing temperature along the proposed critical isochore, we cannot confirm the existence of a liquid-liquid critical point. Our simulations suggest that the parameters previously reported are not a true liquid-liquid critical point and we find no evidence of two-phase coexistence in its vicinity. It is shown that very long simulations (on the order of 8 μs for 500 molecules) are necessary to obtain well converged density distributions for deeply supercooled water and this is especially important if one is seeking direct evidence of a two-phase region.