Corresponding-states behavior of a dipolar model fluid with variable dispersion interactions and its relevance to the anomalies of hydrogen fluoride

被引:3
|
作者
Weiss, Volker C. [1 ]
Leroy, Frederic [2 ,3 ]
机构
[1] Univ Bremen, Bremen Ctr Computat Mat Sci, Fallturm 1, D-28359 Bremen, Germany
[2] Tech Univ Darmstadt, Eduard Zintl Inst Anorgan & Phys Chem, Alarich Weiss Str 8, D-64287 Darmstadt, Germany
[3] Univ Kassel, Inst Chem, Heinrich Plett Str 40, D-34132 Kassel, Germany
来源
JOURNAL OF CHEMICAL PHYSICS | 2016年 / 144卷 / 22期
关键词
LIQUID-VAPOR INTERFACE; PARTICLE MESH EWALD; HARD-SPHERE FLUIDS; SURFACE-TENSION; PHASE-BEHAVIOR; MONTE-CARLO; MOLECULAR SIMULATION; CRITICAL PARAMETERS; CANONICAL ENSEMBLE; IONIC LIQUIDS;
D O I
10.1063/1.4953365
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
More than two decades ago, the elusiveness of a liquid-vapor equilibrium and a corresponding critical point in simulations of the supposedly simple model of dipolar hard spheres came as a surprise to many liquid matter theorists. van Leeuwen and Smit [Phys. Rev. Lett. 71, 3991 (1993)] showed that a minimum of attractive dispersion interactions among the dipolar particles may be needed to observe regular fluid behavior. Here, we adopt their approach and use an only slightly modified model, in which the original point dipole is replaced by a dipole moment produced by charges that are separated in space, to study the influence of dispersion interactions of variable strength on the coexistence and interfacial properties of a polar fluid. The thermophysical properties are discussed in terms of Guggenheim's corresponding-states approach. In this way, the coexistence curve, the critical compressibility factor, the surface tension, Guggenheim's ratio, and modifications of Guldberg's and Trouton's rules (related to the vapor pressure and the enthalpy of vaporization) are analyzed. As the importance of dispersion is decreased, a crossover from simple-fluid behavior to that characteristic of strongly dipolar systems takes place; for some properties, this transition is monotonic, but for others it occurs non-monotonically. For strongly dipolar systems, the reduced surface tension is very low, whereas Guggenheim's ratio and Guldberg's ratio are found to be high. The critical compressibility factor is smaller, and the coexistence curve is wider and more skewed than for simple fluids. For very weak dispersion, liquid-vapor equilibrium is still observable, but the interfacial tension is extremely low and may, eventually, vanish marking the end of the existence of a liquid phase. We discuss the implications of our findings for real fluids, in particular, for hydrogen fluoride. Published by AIP Publishing.
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页数:13
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