Nonsingular Hankel functions as a new basis for electronic structure calculations

• Published in: Journal of mathematical physics 1998-06, Vol.39 (6), p.3393-3425
• Main Authors: Bott, E., Methfessel, M., Krabs, W., Schmidt, P. C.
• Format: Article
• Language: English
• ISSN: 0022-2488; 1089-7658
• DOI: 10.1063/1.532437

As a basis for electronic structure calculations, Gaussians are inconvenient because they show unsuitable behavior at larger distances, while Hankel functions are singular at the origin. This paper discusses a new set of special functions which combine many of the advantageous features of both families. At large distances from the origin, these “smoothed Hankel functions” resemble the standard Hankel functions and therefore show behavior similar to that of an electronic wave function. Near the origin, the functions are smooth and analytical. Analytical expressions are derived for two-center integrals for the overlap, the kinetic energy, and the electrostatic energy between two such functions. We also show how to expand such a function around some point in space and discuss how to evaluate the potential matrix elements efficiently by numerical integration. This supplies the elements needed for a practical application in an electronic structure calculation.