ωB97X-3c: A composite range-separated hybrid DFT method with a molecule-optimized polarized valence double-ζ basis set

A new composite density functional theory (DFT) method is presented. It is based on omega B97X-V as one of the best-performing density functionals for the GMTKN55 thermochemistry database and completes the family of 3c methods toward range-separated hybrid DFT. This method is consistently available for all elements up to Rn (Z = 1-86). Its further key ingredients are a polarized valence double-zeta (vDZP) Gaussian basis set, which was fully optimized in molecular DFT calculations, in combination with large-core effective core potentials and a specially adapted D4 dispersion correction. Unlike most existing double-zeta atomic orbital sets, vDZP shows only small basis set superposition errors (BSSEs) and can compete with standard sets of triple-zeta quality. Small residual BSSE effects are efficiently absorbed by the D4 damping scheme, which overall eliminates the need for an explicit treatment or empirical corrections for BSSE. Thorough tests on a variety of thermochemistry benchmark sets show that the new composite method, dubbed omega B97X-3c, is on par with or even outperforms standard hybrid DFT methods in a quadruple-zeta basis set at a small fraction of the computational cost. Particular strengths of this method are the description of non-covalent interactions and barrier heights, for which it is among the best-performing density functionals overall. Published under an exclusive license by AIP Publishing.

Automated summary

Introduces a new composite density functional theory (DFT) method based on omega B97X-V, one of the best-performing density functionals for the GMTKN55 thermochemistry database. This method is consistently available for all elements up to Rn (Z = 1-86) and utilizes a polarized valence double-zeta (vDZP) Gaussian basis set, large-core effective core potentials, and a specially adapted D4 dispersion correction.