Department for the Modelling of Physico-Chemical Processes, Faculty of Chemistry, MCS University, 20031 Lublin, Poland.
Phys Rev E. 2017 Jan;95(1-1):012145. doi: 10.1103/PhysRevE.95.012145. Epub 2017 Jan 23.
Using Monte Carlo simulation methods in the grand-canonical ensemble, we have studied the phase behavior of three-dimensional symmetric binary mixtures of Lennard-Jones particles. We have also elucidated the effects of geometric and energetic nonadditivity on the phase behavior. Phase diagrams for several systems have been evaluated. We have demonstrated that in completely miscible mixtures the geometrical nonadditivity (negative as well as positive) stabilizes a liquid phase leading to a gradual increase of the critical temperature. The mechanism leading to such behavior is different when the system shows negative and positive geometrical nonadditivity. In the case of systems with negative energetic nonadditivity, which may exhibit demixing transition in the liquid phase, their phase behavior is also strongly affected by the geometric non-additivity. The systems with negative geometric nonadditivity have been demonstrated to show reentrant miscibility, while those with positive geometric nonadditivity show enhanced tendency toward mixing at sufficiently high temperatures. We have evaluated phase diagrams for several systems.
我们使用巨正则系综中的蒙特卡罗模拟方法研究了三维对称 Lennard-Jones 粒子二元混合物的相行为。我们还阐明了几何和能量非加性对相行为的影响。评估了几个系统的相图。我们证明，在完全混溶性混合物中，几何非加性（负加性和正加性）稳定了液相，导致临界温度逐渐升高。当系统表现出负几何非加性和正几何非加性时，导致这种行为的机制是不同的。对于具有负能量非加性的系统，其在液相中可能表现出分相转变，其相行为也受到几何非加性的强烈影响。具有负几何非加性的系统表现出再进入混溶性，而具有正几何非加性的系统在足够高的温度下表现出增强的混合趋势。我们已经评估了几个系统的相图。
