Serially Improved GTOs for Molecular Applications (SIGMA): basis sets from monovalent ions

Abstract

A new family of ionic basis sets, denoted iσXZ1, is presented for molecular calculations on systems containing monovalent ions. The basis sets extend the SIGMA family by explicitly accounting for the different electronic structure of cations and anions. Auxiliary basis sets for resolution-of-the-identity calculations are also developed for the Coulomb term. The performance of the proposed basis sets is assessed for alkali-halide clusters. Compared with conventional basis sets, iσXZ1 provides an accurate description of structural, energetic, and electronic properties while showing remarkable robustness against near-linear dependencies, allowing stable calculations on systems containing up to 792 NaCl units. These features make the iσXZ1 family a reliable and efficient alternative for large-scale calculations on ionic systems.