Probing basis set requirements for calculating hyperfine coupling constants

Abstract

A series of basis sets optimized for the calculation of the hyperfine coupling constant is proposed. The pcH-n basis sets are defined in qualities from double-ζ to pentuple-ζ for the elements H to Ar. They are derived from the polarization consistent basis sets by addition of two tight s-functions and one tight p-, d-, and f-function and are shown to provide an exponential convergence toward the complete basis set limit, and they have significantly lower basis set errors than other commonly used basis sets for a given ζ quality. The pcH basis sets display very similar basis set convergence with a range of density functional theory methods and may also be suitable for wave function based methods.