title: Implementation of nuclear gradients of range-separated hybrid density functionals and benchmarking on rotational constants for organic molecules.
abstract: We have implemented the nuclear gradient for several range-separated hybrid density functionals in the general quantum chemistry code ORCA. To benchmark the performance, we have used a recently published set of back-corrected gas phase rotational constants, which we extended by three molecules. In our evaluation, CAM-B3LYP-D3 and ωB97X-D3 show great accuracy, and are surpassed by B2PLYP-D3 only. Lower-cost alternatives to quadruple-ζ basis set-based calculations, among them a smaller basis set and the use of resolution-of-the-identity approaches, are assessed and shown to yield acceptable deviations. In addition, the Hartree-Fock-based back-correction method is compared to a density functional theory alternative, which largely shows consistency between the two. A new, well-performing, spin-component scaled MP2 variant is designed and discussed, as well.
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstr. 4, D-53115, Bonn, Germany; International NRW Graduate School of Chemistry, Wilhelm-Klemm-Str. 10, D-48149, Münster, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Risthaus
authors.forename: Marc
authors.initials: M
authors.lastname: Steinmetz
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme
keywords: benchmark; density functional theory; molecular structure; range-separated hybrids; spin-component scaled MP2