title: Relativistic two-component calculations of electronic g-tensors that include spin polarization.
abstract: The first two-component relativistic density-functional approach for the calculation of electronic g-tensors is reported that includes spin polarization using noncollinear spin-density functionals. The method is based on the relativistic Douglas-Kroll-Hess Hamiltonian and has been implemented into the ReSpect program package. Using three self-consistent-field calculations with orthogonal orientations of total magnetization J, the full g-matrix may be obtained. In contrast to previous spin-restricted two-component treatments, results with the new approach agree excellently with spin-polarized one-component calculations for light-atom radicals. Additionally, unlike one-component approaches, the method also reproduces successfully the negative deltag(parallel)-values of heavy-atom 2sigma radicals and the negative deltag(perpendicular) components in cysteinyl. The new method removes effectively the dilemma existing up to now regarding the simultaneous inclusion of spin polarization and higher-order spin-orbit effects in g-tensor calculations. It is straightforwardly applicable to higher than doublet spin multiplicities and has been implemented with hybrid functionals.
authors.affiliation: Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany.
authors.forename: Irina
authors.initials: I
authors.lastname: Malkin
authors.forename: Olga L
authors.initials: OL
authors.lastname: Malkina
authors.forename: Vladimir G
authors.initials: VG
authors.lastname: Malkin
authors.forename: Martin
authors.initials: M
authors.lastname: Kaupp