BSSE-corrected consistent Gaussian basis sets of triple-zeta valence quality of the lanthanides La-Lu for solid-state calculations.

Abstract

Consistent basis sets of triple-zeta valence quality for the elements La-Lu were derived for periodic quantum-chemical solid-state calculations. They are an extension of the pob-TZVP-rev2 [D. Vilela Oliveira, et al., J. Comput. Chem. 2019, 40(27), 2364-2376], [J. Laun and T. Bredow, J. Comput. Chem. 2021, 42(15), 1064-1072], [J. Laun and T. Bredow, J. Comput. Chem. 2022, 43(12), 839-846] basis sets and are based on the fully relativistic effective core potentials 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 in crystalline systems. The contraction scheme, orbital exponents, and contraction coefficients were optimized in order to ensure robust and stable self-consistent-field 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-TZV-rev2 than with standard basis sets available from the CRYSTAL basis set database. After augmentation with single diffuse s- and p-functions, reference plane-wave band structures of metals can be accurately reproduced.