Multipole-based distance-dependent screening of Coulomb integrals

Abstract

We derive a new estimate for two-electron repulsion integrals (ERIs), when evaluated within a local atomic basis set. It is based on the multipole expansion and provides a rigorous upper bound of an ERI for well-separated charge distributions. The scheme is generally applicable in any formalism that uses ERIs. We employ it here to screen for potentially negligible contributions in the calculation of the Fock exchange matrix. Using Gaussian basis functions, we show that the estimate allows us to accelerate the construction of the exchange matrix by up to a factor of two without introducing further approximations.