Two-component relativistic hybrid density functional computations of nuclear spin-spin coupling tensors using Slater-type basis sets and density-fitting techniques

Abstract

Computations of indirect nuclear spin-spin coupling constants using two-component relativistic density functional theory with a hybrid functional are reported. The program implementation makes use of a Slater-type orbital expansion of the molecular orbitals and the zeroth-order regular approximation for the treatment of relativistic effects. Exact exchange terms in the Kohn-Sham response kernel were computed using a fitting procedure. Computations with the PBE0 hybrid functional were carried out for heavy-atom-ligand-one-bond couplings in PbH(4), Pb(CH(3))(2)H(2), Pb(CH(3))(3)H, three platinum complexes, the interhalogen diatomics such as ClF, ClBr, ClI, BrF, BrI, IF, and the series Tl-X with X=F, Cl, Br, I. The hybrid functional computations performed very well. In particular, for the isotropic coupling and the coupling anisotropy of Tl-X, the PBE0 hybrid functional yielded considerably improved agreement with experiment.