Widom line and dynamical crossovers as routes to understand supercritical water

被引:139
作者
Gallo, P. [1 ]
Corradini, D. [2 ,3 ]
Rovere, M. [1 ]
机构
[1] Univ Roma Tre, Dipartimento Matemat & Fis, I-00146 Rome, Italy
[2] Boston Univ, Ctr Polymer Studies, Boston, MA 02215 USA
[3] Boston Univ, Dept Phys, Boston, MA 02215 USA
关键词
MOLECULAR-DYNAMICS; CHEMICAL-REACTIONS; LIQUID-PHASE; TRANSITION; VISCOSITY; SYSTEMS; FLUID; H2O;
D O I
10.1038/ncomms6806
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Supercritical water is fundamental in many fields of applications and a precise characterization of the supercritical state is of uttermost importance for this liquid. In a fluid, when moving from the critical point into the single-phase region, the thermodynamic response functions show maxima reminiscent of the critical divergence. Here we study the thermodynamic properties of water in the supercritical region by analysing both available experimental data and our computer simulation results. We find that the lines connecting the maxima of the response functions converge on approaching the critical point in a single line, the Widom line. We further show that the Widom line coincides with a crossover from a liquid-like to a gas-like behaviour clearly visible in the transport properties. These thermodynamic and dynamic features show that the supercritical state in water is far more complex than what was so far believed, indicating a new perspective in the characterization of the thermodynamics of this state.
引用
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页数:6
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