CCUS and Acid Gas Entity, Liquefied Natural Gas Department, Exploration Production, TotalEnergies S.E., 92078 Paris, France.
Engineering Thermodynamics, Process & Energy Department, Faculty of Mechanical, Maritime and Materials Engineering, Delft University of Technology, Leeghwaterstraat 39, Delft 2628CB, The Netherlands.
J Chem Inf Model. 2021 Aug 23;61(8):3752-3757. doi: 10.1021/acs.jcim.1c00652. Epub 2021 Aug 12.
We present several new major features added to the Monte Carlo (MC) simulation code Brick-CFCMC for phase- and reaction equilibria calculations (https://gitlab.com/ETh_TU_Delft/Brick-CFCMC). The first one is thermodynamic integration for the computation of excess chemical potentials (μ). For this purpose, we implemented the computation of the ensemble average of the derivative of the potential energy with respect to the scaling factor for intermolecular interactions (). Efficient bookkeeping is implemented so that the quantity is updated after every MC trial move with negligible computational cost. We demonstrate the accuracy and reliability of the calculation of μ for sodium chloride in water. Second, we implemented hybrid MC/MD translation and rotation trial moves to increase the efficiency of sampling of the configuration space. In these trial moves, short Molecular Dynamics (MD) trajectories are performed to collectively displace or rotate all molecules in the system. These trajectories are accepted or rejected based on the total energy drift. The efficiency of these trial moves can be tuned by changing the time step and the trajectory length. The new trial moves are demonstrated using MC simulations of a viscous fluid (deep eutectic solvent).
我们介绍了为相平衡和反应平衡计算而添加到蒙特卡罗（MC）模拟代码 Brick-CFCMC 的几个新的主要功能（https://gitlab.com/ETh_TU_Delft/Brick-CFCMC）。第一个是用于计算超额化学势（μ）的热力学积分。为此，我们实现了计算对分子间相互作用的缩放因子的势能导数的集合平均值（）。我们实现了高效的簿记，以便在每次 MC 尝试移动后，用可忽略的计算成本更新数量。我们证明了在水中计算氯化钠μ的准确性和可靠性。其次，我们实现了 MC/MD 平移和旋转尝试移动，以提高配置空间采样的效率。在这些尝试移动中，执行短的分子动力学（MD）轨迹以集体地置换或旋转系统中的所有分子。这些轨迹根据总能量漂移来接受或拒绝。通过改变时间步长和轨迹长度可以调整这些尝试移动的效率。使用粘性流体（深共晶溶剂）的 MC 模拟演示了新的尝试移动。
