Department of Chemical Engineering, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
J Chem Phys. 2012 Apr 7;136(13):134108. doi: 10.1063/1.3693328.
We present a simulation method for direct computation of chemical potentials in multicomponent systems. The method involves application of a field to generate spatial gradients in the species number densities at equilibrium, from which the chemical potential of each species is theoretically estimated. A single simulation yields results over a range of thermodynamic states, as in high throughput experiments, and the method remains computationally efficient even at high number densities since it does not involve particle insertion at high densities. We illustrate the method by Monte Carlo simulations of binary hard sphere mixtures of particles with different sizes in a gravitational field. The results of the gradient Monte Carlo method are found to be in good agreement with chemical potentials computed using the classical Widom particle insertion method for spatially uniform systems.
我们提出了一种用于直接计算多组分系统化学势的模拟方法。该方法涉及应用场在平衡时生成物种数密度的空间梯度，从中理论估计每种物质的化学势。单次模拟即可在高通量实验中产生一系列热力学状态下的结果，并且该方法即使在高密度下也保持计算效率，因为它不需要在高密度下进行粒子插入。我们通过在重力场中对不同大小的粒子进行二元硬球混合物的蒙特卡罗模拟来说明该方法。梯度蒙特卡罗方法的结果与空间均匀系统中使用经典 Widom 粒子插入方法计算的化学势吻合良好。
