Gaussian Basis Sets for Solid-State Calculations
At almost every level of theory, the accuracy of a quantum-chemical calculation strongly depends on the quality of the basis functions used to expand the molecular or crystalline orbitals. Unlike a plane-wave basis, contracted Gaussian basis functions are not universal: a separate basis set must be developed for each element in the periodic table. For molecular calculations, a large variety of standard Gaussian basis sets at different quality levels is available. These sets generally contain very small orbital exponents (below 0.1). In periodic systems, the overlap integrals between Bloch functions are larger in absolute value than their molecular counterparts. If the basis functions are too diffuse, the overlap matrix develops small or negative eigenvalues and the basis becomes linearly dependent. Specialized basis sets optimized for solid-state calculations are therefore required.
The pob Basis Sets
Together with Daniel Vilela Oliveira and Thomas Bredow, I developed the pob-TZVP basis sets: consistent, all-electron Gaussian basis sets of triple-zeta valence with polarization quality for periodic calculations with the CRYSTAL code. The sets are derived from the molecular Ahlrichs def2-TZVP standard, with exponents and contraction coefficients reoptimized for robust SCF convergence across a wide range of ionic, semiconducting, and metallic solids.
The original pob-TZVP and pob-TZVPP sets (2013) were followed by the revised pob-TZVP-rev2 and pob-DZVP-rev2 sets (2019), which incorporate a BSSE correction scheme based on counterpoise energies of hydride dimers. The revised sets show significantly reduced and more consistent basis set superposition error across the periodic table, with improved portability and SCF stability. Both generations are fully published and peer-reviewed.
The pob basis sets are available through the CRYSTAL program package basis set library, and are in active use by the solid-state quantum chemistry community. Please cite the relevant papers below if you use them.
Citations
pob-TZVP and pob-TZVPP (original):
Peintinger, M. F., Oliveira, D. V. and Bredow, T. (2013), Consistent Gaussian basis sets of triple-zeta valence with polarization quality for solid-state calculations. J. Comput. Chem., 34: 451–459. doi: 10.1002/jcc.23153
pob-TZVP-rev2 and pob-DZVP-rev2 (revised, with BSSE correction):
Vilela Oliveira, D., Laun, J., Peintinger, M. F. and Bredow, T. (2019), BSSE-correction scheme for consistent Gaussian basis sets of double- and triple-zeta valence with polarization quality for solid-state calculations. J. Comput. Chem., 40: 2364–2376. doi: 10.1002/jcc.25973
Full descriptions and benchmark results are available on the Publications page.