Toward optimal-scaling DFT: stochastic Hartree theory in the thermodynamic and complete basis set limits at arbitrary temperature

Abstract

We present the first mathematical analysis of stochastic density functional theory (DFT) in the context of the Hartree approximation. We motivate our analysis via the notion of nearly-optimal or $\tilde{O}(n)$ scaling with respect to the number $n$ of computational degrees of freedom, independent of the number of electrons, in both the thermodynamic and complete basis set limits. Indeed, the promise of such scaling is the primary motivation for stochastic DFT relative to conventional orbital-based approaches, as well as deterministic orbital-free alternatives. We highlight three key targets for mathematical attention, which are synthesized in our algorithm and analysis. First, we identify a particular stochastic estimator for the Hartree potential whose sample complexity is essentially independent of the discretization size. Second, we reformulate the self-consistent field iteration as a stochastic mirror descent method where the Fermi-Dirac entropy plays the role of the Bregman potential, and we prove a nearly discretization-independent bound on the number of iterations needed to reach fixed accuracy. Third, motivated by the estimator, we introduce a novel pole expansion scheme for the square-root Fermi-Dirac operator, preserving $\tilde{O}(n)$ cost per mirror descent iteration even in the complete basis set limit. Combining these ingredients, we establish nearly-optimal scaling in both limits of interest under reasonable assumptions on the basis sets chosen for discretization. Extensive numerical experiments on problems with as many as $10^{6}$ degrees of freedom validate our algorithm and support the theory of nearly-optimal scaling.