A Monte Carlo method for simulating associating fluids

Abstract

We present association biased Monte Carlo (ABMC), a Monte Carlo method, which is ergodic, microscopically reversible, and specifically designed to simulate associating fluids with long‐ranged center‐to‐center interactions. The canonical ensemble (NVT) algorithm biases sampling to regions of configuration space where particle association is likely to occur, and provides efficient simulation of associating fluids over a broad range of densities. The usual canonical ensemble (NVT) thermodynamic variables (ensemble average internal energy and pressure), as well as the pair distribution functions are presented. The distributions of associated clusters are presented at a selection of state points and are compared with predictions of thermodynamic perturbation theory for the model system. We also present the simulation results for a symmetric, binary associating fluid with a single site on each particle.