Thapar Vikram, Escobedo Fernando A
School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853, USA.
J Chem Phys. 2015 Dec 28;143(24):244113. doi: 10.1063/1.4938248.
In this work, a method is proposed to simultaneously compute the transition rate constant and the free energy profile of a rare event along an order parameter connecting two well-defined regions of phase space. The method employs a forward flux sampling technique in combination with a mean first passage time approach to estimate the steady state probability and mean first passage times. These quantities are fitted to a Markovian model that allows the estimation of the free energy along the chosen order parameter. The proposed technique is first validated with two test systems (an Ising model and a model potential energy surface) and then used to study the solid-phase homogeneous nucleation of selected polyhedral particles.
在这项工作中，我们提出了一种方法，用于同时计算沿着连接相空间两个明确定义区域的序参量发生罕见事件的跃迁速率常数和自由能分布。该方法采用前向通量采样技术并结合平均首次通过时间方法来估计稳态概率和平均首次通过时间。将这些量拟合到一个马尔可夫模型中，该模型允许沿着所选序参量估计自由能。所提出的技术首先在两个测试系统（一个伊辛模型和一个模型势能面）上进行验证，然后用于研究选定多面体颗粒的固相均匀成核。
