Cochran T W, Chiew Y C
Department of Chemical and Biochemical Engineering, Rutgers University, Piscataway, New Jersey 08854, USA.
J Chem Phys. 2006 Jun 14;124(22):224901. doi: 10.1063/1.2203633.
A perturbed chain equation of state for the solid phase has been derived. Although the equation is general with respect to intermolecular potential, we incorporate the Lennard-Jones potential in this work in order to compare results from the model with available Monte Carlo simulation data. Two forms of the radial distribution function for the hard-sphere solid chain reference state are used in the model. First, a theoretically rigorous approach is taken by using a correlation of actual solid-phase Monte Carlo hard-sphere chain data for the radial distribution function. This results in good agreement with the Monte Carlo data only at high density. Second, a simple extended-density approximation was used for the radial distribution function. This second approach was found to work well across the entire density range including the vicinity of the solid-fluid equilibrium.
已经推导了固相的微扰链状态方程。尽管该方程对于分子间势是通用的，但为了将模型结果与现有的蒙特卡罗模拟数据进行比较，我们在这项工作中采用了 Lennard-Jones 势。模型中使用了硬球固体链参考态的两种径向分布函数形式。首先，通过使用实际固相蒙特卡罗硬球链数据对径向分布函数的相关性，采用了一种理论上严格的方法。这仅在高密度下与蒙特卡罗数据取得了良好的一致性。其次，对径向分布函数使用了一种简单的扩展密度近似。发现第二种方法在包括固液平衡附近在内的整个密度范围内都能很好地工作。
