Multi-particle sampling in Monte Carlo simulations on fluids: efficiency and extended implementations

Abstract

Various technical aspects affecting the efficiency of a recently proposed novel Monte Carlo (MC) simulation scheme based on biased simultaneous displacements/rotations of all particles of the system are investigated using two polarisable models of water, the Chialvo–Cummings and Brodholt–Sampoli–Vallauri models, as a test case. Necessary expressions for polarisable site–site interaction models are derived along with a novel smoothing of the potential at the cut-off distance. In addition to the common thermodynamic and structural properties, the mean-squared displacements, rotation relaxation, speed of equilibration (translational order parameter, TOP) and autocorrelation coefficients have been computed as well, in order to assess the efficiency of the method. Gain in speed by parallelisation has also been examined. Performance of the method is coumpared with both the standard one-particle move method and the available approximate methods. It is shown that the multi-particle move (MPM) method performs about by a factor of 10 faster for the systems considered when compared with the common MC scheme, and several times faster when compared with the approximate methods. Parallelised codes of the MPM method may then perform about 70 times faster than the conventional MC. These conclusions hold true for the system size simulated (N = 256) because the efficiency of the multi-particle method depends on the size of the system: its efficiency even increases with increasing number of particles.

Keywords:

• multi-particle move
• MC
• parallelisation
• reaction field
• polarisable models of water

Acknowledgements

This work was supported by the Grand Agency of the Academy of Sciences of the Czech Republic (grant no. IAA400720802). Valuable discussions with Dr M. Predota, University of South Bohemia, are also greatly acknowledged.