Development of a grand canonical-kinetic Monte Carlo scheme for simulation of mixtures

Abstract

A rejection-free methodology-based kinetic Monte Carlo (kMC) method has been developed in the grand canonical ensemble to simulate fluid mixtures. It comprises two different moves: entropic displacement of a selected molecule (based on the Rosenbluth algorithm) in the volume space of the system, and exchange of molecules with the surroundings (insertion or deletion). These two moves are made sequentially with M displacement moves followed by one exchange. The displacement moves are treated as sub-NVT sequences within a grand canonical ensemble. The procedure for deletion or insertion of a molecule is either, based on the Rosenbluth algorithm, or on a direct comparison, in which the average activity of one component is compared with its specified activity. The components are chosen either with equal probability or with a probability proportional to their density. The implementation of rejection-free kMC is much simpler than the Metropolis importance sampling MC procedure, which requires three different types of move, all of which must be tested for acceptance or rejection. The new scheme has been evaluated by applying it to fluid argon and to an equimolar mixture of methane, ethane and propane.

Keywords:

• Kinetic Monte Carlo
• grand canonical ensemble
• chemical potential
• mixture

Funding

This work was supported by the Australian Research Council [grant number DP160103540].

Disclosure statement

No potential conflict of interest was reported by the authors.