Projected q-Shells for Nested Gausslet Bases

Abstract

Electronic-structure calculations require a finite representation of both the electronic wave functions and their Coulomb interaction. Conventional compact basis sets lead to a four-index interaction. Gausslet basis sets are one of a very small number of approaches that allow a much smaller two-index interaction, similar to a real-space grid, but with far fewer points. The continuing challenge in their development is reducing further the number of functions needed while maintaining high accuracy. Here we introduce projected q-shells (PQS), an improvement to the nested Cartesian gausslets of White and Lindsey. Their standard nesting construction divides a joining shell into disjoint faces, edges, and corners, reducing its polynomial completeness from order q to order q-2. PQS approximately restores the two lost orders. In terms of completeness, we prove that for an ideal, undistorted parent, the span of the PQS basis is equivalent to an overcomplete basis of overlapping patches. Coordinate distortions, which are always used in practice, harm this equivalence only slightly. The moment properties that allow two-index interactions also become inexact, even without distortion, but we show that the improvement in order more than makes up for this loss. For similar basis sizes, PQS gives smaller one-electron and interaction errors on small molecules, such as H2+, H2, and C2, than standard nesting. The improvement is largest for more compact bases with smaller q.