BSSE‐corrected consistent Gaussian basis sets of triple‐zeta valence with polarization quality of the sixth period for solid‐state calculations

Abstract

Consistent basis sets of triple-zeta valence with polarization quality for the elements Cs-Po were derived for periodic quantum-chemical solid-state calculations. They are an extension of the pob-TZVP-rev2 [Vilela Oliveira, D.; Laun, J.; Peintinger, M. F. and Bredow, T., J. Comput. Chem., 2019, 40 (27), 2364-2376] basis sets and are based on the fully relativistic effective core potentials (ECPs) of the Stuttgart/Cologne group and on the def2-TZVP valence basis of the Ahlrichs group. The basis sets are constructed to minimize the basis set superposition error (BSSE) in crystalline systems. The contraction scheme, the orbital exponents, and contraction coefficients were optimized in order to ensure robust and stable self-consistent-field (SCF) convergence for a set of compounds and metals. For the applied PW1PW hybrid functional, the average deviations of the calculated lattice constants from experimental references are smaller with pob-TZVP-rev2 than with standard basis sets available from the CRYSTAL basis set database.