Sweatman M B
Department of Chemical and Process Engineering, University of Strathclyde, Glasgow, G1 1XJ, United Kingdom.
Phys Rev E Stat Nonlin Soft Matter Phys. 2005 Jul;72(1 Pt 2):016711. doi: 10.1103/PhysRevE.72.016711. Epub 2005 Jul 20.
A self-referential Monte Carlo method is described for calculating the free energy of crystalline solids. All Monte Carlo methods for the free energy of classical crystalline solids calculate the free-energy difference between a state whose free energy can be calculated relatively easily and the state of interest. Previously published methods employ either a simple model crystal, such as the Einstein crystal, or a fluid as the reference state. The self-referential method employs a radically different reference state; it is the crystalline solid of interest but with a different number of unit cells. So it calculates the free-energy difference between two crystals, differing only in their size. The aim of this work is to demonstrate this approach by application to some simple systems, namely, the face centered cubic hard sphere and Lennard-Jones crystals. However, it can potentially be applied to arbitrary crystals in both bulk and confined environments, and ultimately it could also be very efficient.
描述了一种用于计算晶体固体自由能的自参考蒙特卡罗方法。所有用于经典晶体固体自由能的蒙特卡罗方法都是计算自由能相对容易计算的状态与感兴趣状态之间的自由能差。先前发表的方法要么采用简单的模型晶体，如爱因斯坦晶体，要么采用流体作为参考状态。自参考方法采用了一种截然不同的参考状态；它是感兴趣的晶体固体，但具有不同数量的晶胞。因此，它计算的是两个仅大小不同的晶体之间的自由能差。这项工作的目的是通过应用于一些简单系统，即面心立方硬球晶体和 Lennard-Jones 晶体，来证明这种方法。然而，它有可能应用于块状和受限环境中的任意晶体，并且最终也可能非常高效。
