New Features of the Open Source Monte Carlo Software Brick-CFCMC: Thermodynamic Integration and Hybrid Trial Moves

Abstract

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^ex). 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 ($⟨\frac{\partial U}{\partial \lambda }⟩$). Efficient bookkeeping is implemented so that the quantity $\frac{\partial U}{\partial \lambda }$ is updated after every MC trial move with negligible computational cost. We demonstrate the accuracy and reliability of the calculation of μ^ex 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).