论文标题
显式溶剂离子模型中的流体流体相行为:硬晶状体溶剂分子
Fluid-fluid phase behaviour in the explicit solvent ionic model: hard spherocylinder solvent molecules
论文作者
论文摘要
我们研究了显式溶剂模型的流体流体相变,该模型表示为离子液和中性硬晶状体(HSC)的限制原始模型(RPM)的混合物。为此,我们结合了两种理论方法,即刻度粒子理论(SPT)和关联平均球形近似(AMSA)。尽管SPT足以对考虑到硬核相互作用的参考系统提供相当好的描述,但已知AMSA在治疗离子之间的库仑相互作用方面有效。或者,我们还使用平均球形近似(MSA)进行比较。通常,这两个近似值都会为相图带来相似的定性结果:共存包膜的区域变得更广泛,并且在压力增加时向更大的密度和更高的温度转移。但是,AMSA和MSA产生不同的浓度依赖性,即与MSA相反,AMSA相图表明,高密度相主要由所考虑的所有压力组成的离子组成。为了证明溶剂分子非球体对流体流体相变的影响,我们考虑了一种“等效”混合物,其中HSC颗粒被同一体积的硬球(HS)代替。据观察,在HSC溶剂(RPM-HSC模型)的情况下,相共存的区域比球形形状(RPM-HS模型)的溶剂分子宽。还发现,RPM-HSC模型中的临界温度高于RPM-HS模型,尽管在MSA中的压力较高,而在AMSA中,这种差异仍然是必不可少的。
We study a fluid-fluid phase transition of the explicit solvent model represented as a mixture of the restricted primitive model (RPM) of ionic fluid and neutral hard spherocylinders (HSC). To this end, we combine two theoretical approaches, i.e., the scale particle theory (SPT) and the associative mean spherical approximation (AMSA). Whereas the SPT is sufficient to provide a rather good description of a reference system taking into account hard-core interactions, the AMSA is known to be efficient in treating the Coulomb interactions between the ions. Alternatively, we also use the mean spherical approximation (MSA) for comparison. In general, both approximations lead to similar qualitative results for the phase diagrams: the region of coexisting envelope becomes broader and shifts towards larger densities and higher temperatures when the pressure increases. However, the AMSA and the MSA produce different concentration dependences, i.e., contrary to the MSA, the AMSA phase diagrams show that the high-density phase mostly consists of the ions for all pressures considered. To demonstrate the effect of asphericity of solvent molecules on the fluid-fluid phase transition, we consider an "equivalent" mixture in which the HSC particles are replaced by hard spheres (HS) of the same volume. It is observed that in the case of HSC solvent (RPM-HSC model), the region of phase coexistence is wider than for the case of the solvent molecules being of spherical shape (RPM-HS model). It is also found that the critical temperature is higher in the RPM-HSC model than in the RPM-HS model, though it becomes the same at higher pressures in the MSA, while in the AMSA this difference remains essential.