title: Electric Field Gradients Calculated from Two-Component Hybrid Density Functional Theory Including Spin-Orbit Coupling.
abstract: An implementation of a four-component density corrected approach for calculations of nuclear electric field gradients (EFGs) in molecules based on the two-component relativistic zeroth-order regular approximation (ZORA) is reported. The program module, which is part of the NWChem package, allows for scalar and spin-orbit relativistic computations of EFGs. Benchmark density functional calculations are reported for a large set of main group diatomic molecules, a set of Cu and Au diatomics, several Ru and Nb complexes, the free uranyl ion, and two uranyl carbonate complexes. Data obtained from nonhybrid as well as fixed and range-separated hybrid functionals are compared. To allow for a chemically intuitive interpretation of the results, a breakdown of the EFGs of selected systems in terms of localized molecular orbitals is given. For CuF, CuCl, AuCl, UO2(2+), and a uranyl carbonate complex, the localized orbital decomposition demonstrates in particular the role of the valence metal d and f shells, respectively, and leads to rather compact analyses. For f orbitals, a Townes-Dailey-like model is set up to assist the analysis.
authors.affiliation: Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd, P.O. Box 999, Mail Stop K8-91 Richland, Washington 99352.
authors.forename: Fredy
authors.initials: F
authors.lastname: Aquino
authors.affiliation: Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd, P.O. Box 999, Mail Stop K8-91 Richland, Washington 99352.
authors.forename: Niranjan
authors.initials: N
authors.lastname: Govind
authors.affiliation: Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd, P.O. Box 999, Mail Stop K8-91 Richland, Washington 99352.
authors.forename: Jochen
authors.initials: J
authors.lastname: Autschbach