Relativistic quintuple-zeta basis sets for the p block

TL;DR

This paper introduces new relativistic quintuple-zeta basis sets for p block elements, optimized for high-accuracy quantum chemical calculations involving heavy elements, and demonstrates their improved convergence and precision over previous basis sets.

Contribution

The paper presents the development and optimization of relativistic quintuple-zeta basis sets for p block elements, enhancing accuracy in heavy element calculations.

Findings

Smooth convergence to basis set limit observed

Improved accuracy in molecular bond lengths and energies

Basis sets available for widespread use

Abstract

Relativistic quintuple-zeta basis sets for the p elements are presented. The basis sets for the occupied spinors were optimized at the Dirac-Coulomb self-consistent field (SCF) level on the ground configurations. Valence and core correlating functions were optimized in multireference SDCI calculations on the ground configuration. Diffuse functions optimized on the anion (or derived from neighboring elements for group 18) are also provided. Basic atomic and molecular properties were used to test the newly developed basis sets. A smooth convergence to the basis set limit is observed with increased basis set quality from the previously available double-zeta, triple-zeta, and quadruple-zeta basis sets to the newly developed quintuple-zeta basis sets for the calculated molecular bond lengths and dissociation energies and for atomic ionization potentials and electron affinities. Use of these basis sets in combination with state-of-the-art approaches for treatment of relativity and correlation will allow significantly increased accuracy in calculations on the heavy elements and their compounds. The basis sets are available at https://doi.org/10.5281/zenodo.18351835.