Correlated Response Calculations of the Spin-Orbit Interaction Contribution to Nuclear Spin-Spin Couplings

摘要

We present ab initio perturbation calculations of the electronic spin-orbit interaction contributions to indirect spin-spin coupling tensors using linear and quadratic response methods. The effects of both the Fermi-contact and the spin-dipole interactions as well as the one- and two-electron spin-orbit interactions are considered for the ~1J_(HX) and ~2J_(HH) couplings in the H_2X (X = O, S, Se, and Te) and HX (X = F, Cl, Br, and I) systems using nonrelativistic multiconfiguration self-consistent-field reference states. Novel second-order spin-orbit-induced contributions to the J tensors due to the magnetic-field dependence of the spin-orbit Hamiltonian are introduced and formulated as linear response functions. Calculations of these contributions are reported for the ~2J_(HH) coupling tensors in the H_2X systems.