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Abstract:
We study a coarse-grained model for a water monolayer that cannot crystallize due to the presence of confining interfaces, such as protein powders or inorganic surfaces. Using both Monte Carlo simulations
and mean field calculations, we calculate three response functions: the isobaric specific heat CP, the isothermal compressibility KT, and the isobaric thermal expansivity αP. At low temperature
T, we find two distinct maxima in CP, KT, and |αP|, all converging toward a liquid-liquid critical point (LLCP) with increasing pressure P. We show that the maximum in CP at higher T is due to the fluctuations of hydrogen (H) bond formation and that the second maximum at lower T is due
to the cooperativity among the H bonds. We discuss a similar effect in KT and |αP|. If this cooperativity were not taken into account, both the lower-T maximum and the LLCP would disappear. However, comparison with recent experiments on water hydrating protein powders provides evidence
for the existence of the lower-T maximum, supporting the hypothesized LLCP at positive P and finite T. The model also predicts that when P moves closer to the critical P the CP maxima move closer in T until they merge at the LLCP. Considering that other scenarios for water are thermodynamically possible, we discuss how an experimental measurement of the changing separation in T between the two maxima of CP as P increases could determine the best scenario for describing water.
