On the possible locus of the liquid–liquid critical point in real water from studies of supercooled water using the TIP4P/Ice model

Abstract

One of the most accepted hypothesis to explain the anomalous behavior of water is the presence of a critical point between two liquids, the liquid–liquid critical point (LLCP), buried within the deep supercooled regime. Unfortunately, such hypothesis is hard to be experimentally confirmed due to fast freezing. Here, we show that the TIP4P/Ice water potential shifted by 400 bar can reproduce with unprecedented accuracy the experimental isothermal compressibility of water and its liquid equation of state for a wide pressure and temperature range. We find, both by extrapolation of response function maxima and by a Maxwell construction, that the location of the model LLCP is consistent with previous calculations. According to the pressure shift needed to recover the experimental behavior of supercooled water, we estimate the experimental LLCP to be located around 1250 bar and 195 K. We use the model to estimate the ice nucleation rate (J) in the vicinity of the hypothesized LLCP experimental location and obtain J = 1024 m−3 s−1. Thereby, experiments where the ratio between the cooling rate and the sample volume is equal or larger than the estimated nucleation rate could probe liquid–liquid equilibrium before freezing. Such conditions are not accessible in common experiments with microdroplets cooled at a few kelvin per second, but they could be, for instance, using nanodroplets of around 50 nm radius observed in a millisecond timescale.