Isotope effects in supercooled H_2O and D_2O and a corresponding-states-like rescaling of the temperature and pressure
arxiv(2024)
摘要
Water shows anomalous properties that are enhanced upon supercooling. The
unusual behavior is observed in both H_2O and D_2O, however with different
temperature dependences for the two isotopes. It is often noted that comparing
the properties of the isotopes at two different temperatures (i.e., a
temperature shift) approximately accounts for many of the observations with a
temperature shift of 7.2 K in the temperature of maximum density being the most
well-known example. However, the physical justification for such a shift is
unclear. Motivated by recent work demonstrating a corresponding-states-like
rescaling for water properties in three classical water models that all exhibit
a liquid-liquid transition and critical point (B. Uralcan, et al., J. Chem.
Phys. 150, 064503 (2019)), the applicability of this approach for reconciling
the differences in temperature- and pressure-dependent thermodynamic properties
of H_2O and D_2O is investigated here. Utilizing previously published data
and equations-of-state for H_2O and D_2O, we show that the available data
and models for these isotopes are consistent with such a low temperature
correspondence. These observations provide support for the hypothesis that a
liquid-liquid critical point, which is predicted to occur at low temperatures
and high pressures, is the origin of many of water's anomalies.
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