Ioffe Physical-Technical Institute of the Russian Academy of Sciences, 26 Polytechnicheskaya, St. Petersburg 194021, Russia.
School of Chemical Engineering, University of Queensland, St. Lucia, Qld 4072, Australia.
J Colloid Interface Sci. 2012 Jan 15;366(1):216-223. doi: 10.1016/j.jcis.2011.09.074. Epub 2011 Oct 2.
Kinetic Monte Carlo (kMC) simulations were carried out to describe the vapour-liquid equilibria of argon at various temperatures. This paper aims to demonstrate the potential of the kMC technique in the analysis of equilibrium systems and its advantages over the traditional Monte Carlo method, which is based on the Metropolis algorithm. The key feature of the kMC is the absence of discarded trial moves of molecules, which ensures larger number of configurations that are collected for time averaging. Consequently, the kMC technique results in significantly fewer errors for the same number of Monte Carlo steps, especially when the fluid is rarefied. An additional advantage of the kMC is that the relative displacement probability of molecules is significantly larger in rarefied regions, which results in a more efficient sampling. This provides a more reliable determination of the vapour phase pressure and density in case of non-uniform density distributions, such as the vapour-liquid interface or a fluid adsorbed on an open surface. We performed kMC simulations in a canonical ensemble, with a liquid slab in the middle of the simulation box to model two vapour-liquid interfaces. A number of thermodynamic properties such as the pressure, density, heat of evaporation and the surface tension were reliably determined as time averages.
采用动力学蒙特卡罗（kMC）模拟方法描述了不同温度下氩气的汽液平衡。本文旨在展示 kMC 技术在平衡系统分析中的潜力及其相对于基于 Metropolis 算法的传统蒙特卡罗方法的优势。kMC 的主要特点是不存在分子被丢弃的试探性运动，这确保了在时间平均中收集到更多的构型。因此，对于相同数量的蒙特卡罗步骤，kMC 技术的误差要小得多，尤其是在流体稀薄的情况下。kMC 的另一个优点是，在稀薄区域中分子的相对位移概率显著增大，这导致了更有效的抽样。这为不均匀密度分布（例如汽液界面或开放表面上吸附的流体）情况下蒸气相压力和密度的更可靠确定提供了依据。我们在正则系综中进行了 kMC 模拟，在模拟盒的中间有一个液体薄片，以模拟两个汽液界面。可靠地确定了作为时间平均值的各种热力学性质，例如压力、密度、蒸发热和表面张力。
