论文标题
硬球中的三元混合物中的流体流体解散和密度异常
Fluid-fluid demixing and density anomaly in a ternary mixture of hard spheres
论文作者
论文摘要
我们报告了用立方体构建的Husimi晶格上定义的离散硬球的三元混合物的宏伟典型解决方案,该晶格在立方晶格上为该系统提供了平均场近似值。该混合物由分别排除到第一个(1NN)和第二个邻居(2NN)的粒子(0NN)和粒子组成,分别为$ z_0 $,$ z_1 $和$ z_2 $组成。我们的解决方案揭示了非常丰富的热力学行为,其两个实心阶段与1NN($ S1 $)或2NN颗粒($ S2 $)和两个流体相关的订购相关,另一个是常规的($ RF $),而另一个具有0NN颗粒($ f0 $ apep)的特征。但是,在大多数相图中,这些流体($ f $)阶段是无法区分的。在所有四个阶段之间都观察到不连续的转变,从而产生了系统中的几个共存表面,其中流体流体和固体固体分离表面。前者受到一系列关键点和三分点的限制(其中$ rf $ - $ f0 $ - $ s2 $ coexist)都在一个特殊点上会议,此后流体 - 流体的共存就变得可稳定了。发现了另一个三分点,连接$ f $ - $ s1 $,$ f $ - $ s2 $和$ s1 $ - $ s2 $共存表面。还可以观察到在三级点点上符合$ f $ - $ s1 $并存的关键$ f $ - $ s1 $。此外,发现了颗粒总密度的最小曲线中的最小值的热力学异常,在活动空间中产生了三个最小密度的表面,具体取决于在计算过程中固定的活性。
We report the grand-canonical solution of a ternary mixture of discrete hard spheres defined on a Husimi lattice built with cubes, which provides a mean-field approximation for this system on the cubic lattice. The mixture is composed by point-like particles (0NN) and particles which exclude up to their first (1NN) and second neighbors (2NN), with activities $z_0$, $z_1$ and $z_2$, respectively. Our solution reveals a very rich thermodynamic behavior, with two solid phases associated with the ordering of 1NN ($S1$) or 2NN particles ($S2$), and two fluid phases, being one regular ($RF$) and the other characterized by a dominance of 0NN particles ($F0$ phase). However, in most part of the phase diagram these fluid ($F$) phases are indistinguishable. Discontinuous transitions are observed between all the four phases, yielding several coexistence surfaces in the system, among which a fluid-fluid and a solid-solid demixing surface. The former one is limited by a line of critical points and a line of triple points (where the phases $RF$-$F0$-$S2$ coexist), both meeting at a special point, after which the fluid-fluid coexistence becomes metastable. Another line of triple points is found, connecting the $F$-$S1$, $F$-$S2$ and $S1$-$S2$ coexistence surfaces. A critical $F$-$S1$ surface is also observed meeting the $F$-$S1$ coexistence one at a line of tricritical points. Furthermore, a thermodynamic anomaly characterized by minima in isobaric curves of the total density of particles is found, yielding three surfaces of minimal density in the activity space, depending on which activity is kept fixed during its calculation.