Optimal sampling efficiency in Monte Carlo simulation with an approximate potential.

Building on the work of Iftimie et al. [J. Chem. Phys. 113, 4852 (2000)] and Gelb [J. Chem. Phys. 118, 7747 (2003)], Boltzmann sampling of an approximate potential (the "reference" system) is used to build a Markov chain in the isothermal-isobaric ensemble. At the end points of the chain, the energy is evaluated at a more accurate level (the "full" system) and a composite move encompassing all of the intervening steps is accepted on the basis of a modified Metropolis criterion. For reference system chains of sufficient length, consecutive full energies are statistically decorrelated and thus far fewer are required to build ensemble averages with a given variance. Without modifying the original algorithm, however, the maximum reference chain length is too short to decorrelate full configurations without dramatically lowering the acceptance probability of the composite move. This difficulty stems from the fact that the reference and full potentials sample different statistical distributions. By manipulating the thermodynamic variables characterizing the reference system (pressure and temperature, in this case), we maximize the average acceptance probability of composite moves, lengthening significantly the random walk between consecutive full energy evaluations. In this manner, the number of full energy evaluations needed to precisely characterize equilibrium properties is dramatically reduced. The method is applied to a model fluid, but implications for sampling high-dimensional systems with ab initio or density functional theory potentials are discussed.