Isotope effects in supercooled H2O and D2O and a corresponding-states-like rescaling of the temperature and pressure

被引:1
|
作者
Kimmel, Greg A. [1 ]
机构
[1] Pacific Northwest Natl Lab, Phys Sci Div, POB 999, Richland, WA 99352 USA
来源
JOURNAL OF CHEMICAL PHYSICS | 2024年 / 160卷 / 19期
关键词
LIQUID-LIQUID TRANSITION; THERMODYNAMIC PROPERTIES; SELF-DIFFUSION; HEAT-CAPACITY; MAXIMUM DENSITY; CRITICAL-POINT; WATER; COMPRESSIBILITY; DEPENDENCE; SINGULARITY;
D O I
10.1063/5.0207719
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Water shows anomalous properties that are enhanced upon supercooling. The unusual behavior is observed in both H2O and D2O, 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 [Uralcan et al., J. Chem. Phys. 150, 064503 (2019)], the applicability of this approach for reconciling the differences in the temperature- and pressure-dependent thermodynamic properties of H2O and D2O is investigated here. Utilizing previously published data and equations-of-state for H2O and D2O, 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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页数:9
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