Improvement of d-d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds.

ABSTRACT: To improve the description of interactions among the localized d, f electrons in transition metals, we have introduced a ligand-field motivated contribution into the Density Functional Tight Binding (DFTB) model. Referred to as DFTB3+U, the approach treats the d, f electron repulsions with rotationally invariant orbital-orbital interactions and a Hartree-Fock model; this represents a major conceptual improvement over the original DFTB3 approach, which treats the d, f-shell interactions in a highly averaged fashion without orbital level of description. The DFTB3+U approach is tested using a series of nickel compounds that feature Ni(ii) and Ni(iii) oxidation states. By using parameters developed with the original DFTB3 Hamiltonian and empirical +U parameters (F0/2/4 Slater integrals), we ob

SUBMITTER: Stepanovic S 

PROVIDER: S-EPMC7737908 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature