Smart darting diffusion Monte Carlo: Applications to lithium ion-Stockmayer clusters.

Abstract

In a recent investigation [K. Roberts et al., J. Chem. Phys. 136, 074104 (2012)], we have shown that, for a sufficiently complex potential, the Diffusion Monte Carlo (DMC) random walk can become quasiergodic, and we have introduced smart darting-like moves to improve the sampling. In this article, we systematically characterize the bias that smart darting moves introduce in the estimate of the ground state energy of a bosonic system. We then test a simple approach to eliminate completely such bias from the results. The approach is applied for the determination of the ground state of lithium ion-n-dipoles clusters in the n = 8-20 range. For these, the smart darting diffusion Monte Carlo simulations find the same ground state energy and mixed-distribution as the traditional approach for n < 14. In larger systems we find that while the ground state energies agree quantitatively with or without smart darting moves, the mixed-distributions can be significantly different. Some evidence is offered to conclude that introducing smart darting-like moves in traditional DMC simulations may produce a more reliable ground state mixed-distribution.