Merikanto Joonas, Zapadinsky Evgeni, Lauri Antti, Napari Ismo, Vehkamäki Hanna
Department of Physical Sciences, University of Helsinki, P.O. Box 64, FIN-00014 University of Helsinki, Finland.
J Chem Phys. 2007 Sep 14;127(10):104303. doi: 10.1063/1.2766719.
We carry out Monte Carlo simulations of physical Lennard-Jones and water clusters and show that the number of physical clusters in vapor is directly related to the virial equation of state. This relation holds at temperatures clearly below the critical temperatures, in other words, as long as the cluster-cluster interactions can be neglected--a typical assumption used in theories of nucleation. Above a certain threshold cluster size depending on temperature and interaction potential, the change in cluster work of formation can be calculated analytically with the recently proposed scaling law. The breakdown of the scaling law below the threshold sizes is accurately modeled with the low order virial coefficients. Our results indicate that high order virial coefficients can be analytically calculated from the lower order coefficients when the scaling law for cluster work of formation is valid. The scaling law also allows the calculation of the surface tension and equilibrium vapor density with computationally efficient simulations of physical clusters. Our calculated values are in good agreement with those obtained with other methods. We also present our results for the curvature dependent surface tension of water clusters.
我们对物理上的 Lennard-Jones 簇和水簇进行了蒙特卡罗模拟,结果表明蒸汽中物理簇的数量与维里状态方程直接相关。这种关系在明显低于临界温度的温度下成立,也就是说,只要簇-簇相互作用可以忽略——这是成核理论中常用的一个典型假设。在取决于温度和相互作用势的某个阈值簇尺寸以上,簇形成功的变化可以用最近提出的标度律进行解析计算。低于阈值尺寸时标度律的失效可以用低阶维里系数精确建模。我们的结果表明,当成簇形成功的标度律有效时,可以从低阶系数解析计算高阶维里系数。该标度律还允许通过对物理簇进行计算效率高的模拟来计算表面张力和平衡蒸汽密度。我们计算的值与用其他方法获得的值非常吻合。我们还给出了水簇曲率相关表面张力的结果。