A Multifaceted Analysis of Angular and Radial Quadratures

Meredith I. Reeves\(^{1}\), Marco Martínez-González\(^{1}\), Paul W. Ayers\(^{1}\), and Farnaz Heidar-Zadeh\(^{2}\)

\(^{1}\) Department of Chemistry and Chemical Biology, McMaster University, 1280 Main St W, Hamilton, Ontario, Canada, L9A 1C7
\(^{2}\) Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, Canada, K7L 3N6

Numerical integration (quadrature) is essential for modern quantum-chemical calculations, especially density-functional theory methods and their post-processing (into atomic charges, bond orders, etc.). Many different integration methods for evaluating molecular properties have been proposed, but the most efficient seems to be the (generalized) Becke integration scheme, where each molecular property is broken into atomic contributions, which are integrated by combining a radial quadrature with an angular/spherical quadrature. We perform a series of comparative studies analyzing available one-dimensional quadratures, accompanying radial transforms, and angular quadratures reported in the literature. Specifically, we investigate how accurate these methods are for approximating integrals associated with the number of electrons, Kohn-Sham kinetic energy, and the dipole and quadrupole moments. In addition, to assess how well the grids compute numerical derivatives, we investigate the Weizsäcker kinetic energy.

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