Efficient Isoparametric Integration over Arbitrary, Space-Filling Voronoi Polyhedra for Electronic-Structure Calculations

Abstract

A numerically efficient, accurate, and easily implemented integration scheme over convex Voronoi polyhedra (VP) is presented for use in {\it ab-initio} electronic-structure calculations. We combine a weighted Voronoi tessellation with isoparametric integration via Gauss-Legendre quadratures to provide rapidly convergent VP integrals for a variety of integrands, including those with a Coulomb singularity. We showcase the capability of our approach by first applying to an analytic charge-density model achieving machine-precision accuracy with expected convergence properties in milliseconds. For contrast, we compare our results to those using shape-functions and show our approach is greater than $10^{5}$ faster and $10^{7}$ more accurate. A weighted Voronoi tessellation also allows for a physics-based partitioning of space that guarantees convex, space-filling VP while reflecting accurate atomic size and site charges, as we show within KKR methods applied to Fe-Pd alloys.