Free-energy landscape and spinodals for the liquid–liquid transition of the TIP4P/2005 and TIP4P/Ice models of water

Continued increases in computational power now make it possible to evaluate the free-energy landscape associated with the first-order liquid–liquid transition in realistic models of water for which an accurate estimate of the liquid–liquid critical point exists, and to explore its change with pressure near the coexistence line. We report the results of 50 μs-long NPT umbrella sampling simulations for two realistic models for water, TIP4P/2005 and TIP4P/ice, 3–9 K below their critical temperatures. The free energy profile at different pressures clearly shows the presence of two well-defined free energy basins and makes it possible to identify the liquid–liquid spinodal points, the limits of stability that define the (temperature dependent) pressure range within which two distinct free energy basins exist. The results show that for temperatures less than 10 K below the critical temperature, metastable states are possible across a very limited pressure interval, information that is relevant to the interpretation of experiments probing the metastable phase behavior of deeply supercooled water in the so-called no-man’s land.