Understanding and Improving the Efficiency of Full Configuration Interaction Quantum Monte Carlo

Abstract

Within Full Configuration Interaction Quantum Monte Carlo, we investigate how the statistical error behaves as a function of the parameters which control the stochastic sampling. We define the inefficiency as a measure of the statistical error per particle sampling the space and per timestep and show there is a sizeable parameter regime where this is minimised. We find that this inefficiency increases sublinearly with Hilbert space size and can be reduced by localising the canonical Hartree--Fock molecular orbitals, suggesting that the choice of basis impacts the method beyond that of the sign problem.