The most compact relativistic prolapse-free (RPF) Gaussian basis sets ever seen are developed here for cesium through radon, providing small- (SRPF) and medium-size (MRPF) alternatives. The largest errors of these basis sets are consistent with the expected quality level. Soon, these new basis sets should be applied in electronic structure calculations of larger molecular systems with a lower computational cost.

Abstract

Relativistic adapted Gaussian basis sets of small and medium sizes are presented in this study for all elements from cesium to radon, including some alternative electron configurations. Both basis sets are made free of variational prolapse, being developed by means of a polynomial version of the generator coordinate Dirac–Fock method. In addition, these sets were designed to be promptly used with two popular finite nuclear models, uniform sphere and Gaussian nuclei. The largest basis set errors found with the uniform sphere nucleus are 27.3 and 10.6 mHartree, respectively, for the small- and medium-size sets. The largest basis set errors obtained with the Gaussian nuclear model are smaller, reaching 23.2 and 7.1 mHartree for the small- and medium-size sets, respectively. Soon, these basis sets will be augmented with polarization functions to be properly used in molecular calculations.