Stochastic algorithms for self-consistent calculations of electronic structures

Abstract

The convergence property of a stochastic algorithm for the self-consistent field (SCF) calculations of electron structures is studied. The algorithm is formulated by rewriting the electronic charges as a trace/diagonal of a matrix function, which is subsequently expressed as a statistical average. The function is further approximated by using a Krylov subspace approximation. As a result, each SCF iteration only samples one random vector without having to compute all the orbitals. We consider the common practice of SCF iterations with damping and mixing. We prove that the iterates from a general linear mixing scheme converge in a probabilistic sense when the stochastic error has a second finite moment.