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.

A database of computed Raman spectra of inorganic compounds with accurate hybrid functionals

“…In the present data records, we compute Raman spectra together with phonon properties at a consistently high level of theory, namely the hybrid functional PBE0 34 , in a linear combination of atomic orbitals, expanded in terms of triple-ζ valence with polarization (pob-TZVP-rev2) Gaussian basis sets 35 , 36 . These approximations are realized using the CRYSTAL code at a relatively low computation cost thanks to its exploitation of lattice symmetry during frequency calculations 37 – 39 .…”

“…Tolerances for Coulomb and exchange integral series were set to 10 −7 Hartree for both Coulomb overlap and penetration, 10 −7 Hartree for exchange overlap, and 10 −9 and 10 −30 Hartree for exchange penetration. Crystalline orbitals were expanded as a linear combination of atomic orbitals, which are described by Gaussian valence triple-ζ with www.nature.com/scientificdata www.nature.com/scientificdata/ polarization (pob-TZVP-rev2) basis sets 35,36 . In DFT the unknown exchange and correlation functional was approximated with the PBE0 hybrid functional, which provides excellent predictions of the experimental Raman spectra of Na 3 PS 4 and quartz-SiO 2 (Tables 1, 2) 34 .…”