Two-sided Bogoliubov inequality to estimate finite size effects in quantum molecular simulations

Abstract

We generalise the two-sided Bogoliubov inequality for classical particles (Delle Site et al. in J Stat Mech Theory Exp 083201, 2017 to systems of quantum particles. As in the classical set-up, the inequality leads to upper and lower bounds for the free energy difference associated with the partitioning of a large system into smaller, independent subsystems. From a thermodynamic modelling point of view, the free energy difference determines the finite size correction needed to consistently treat a small system as a representation of a large system. Applications of the bounds to quantify finite size effects are ubiquitous in physics, chemistry, material science, or biology, to name just a few; in particular, it is relevant for molecular dynamics simulations in which a small portion of a system is usually taken as representative of the idealized large system.

N‐convergence in one–component plasma: Comparison of Coulomb, Ewald, and angular–averaged Ewald potentials

“…Finite size effect, or $$$ N $$$‐dependence, remains one of the major challenges in the atomistic simulation of Coulomb systems. [ 1–4 ] This issue is especially relevant in simulation of degenerate systems because of the fermion sign problem. A widely‐used reweighting method leads to an exponential growth of the statistical error as the number of particles $$$ N $$$ increases.…”