Relativistic quintuple-zeta basis sets for the s block

TL;DR

This paper introduces relativistic quintuple-zeta basis sets for s-block elements, enhancing computational accuracy for heavy atom and molecule calculations by providing optimized functions and demonstrating smooth convergence to the basis set limit.

Contribution

The paper presents newly developed relativistic quintuple-zeta basis sets for s-block elements, optimized for multireference calculations and benchmarking, enabling higher accuracy in heavy atom computations.

Findings

Smooth convergence observed with increased basis set quality

Basis sets improve accuracy in atomic and molecular property calculations

Available for use at specified online repository

Abstract

Relativistic basis sets of quintuple-zeta quality are presented for the s-block elements. The basis sets include SCF exponents for the occupied spinors and for the np shell (the latter is considered here a valence orbital). Valence and core correlating functions were optimized within multireference SDCI calculations for the ground valence configuration. Diffuse functions optimized for the corresponding anions or derived from neighboring elements are also provided. The new basis sets were applied to a range of basic atomic and molecular properties for benchmarking purposes. Smooth convergence to the basis set limit is observed with increased basis set quality from existing double-zeta, triple-zeta, and quadruple-zeta to the newly developed quintuple-zeta basis sets. Use of these basis sets in combination with state-of-the-art approaches for treatment of relativity and correlation will allow achieving higher accuracy and lower uncertainty than previously possible in calculations on heavy atoms and molecules. The basis sets are available at https://doi.org/10.5281/zenodo.17088050.