Treating Spin-Orbit Coupling and Spin-Spin Coupling in the Framework of the Iterative Configuration Expansion Selected CI.

Spin-adapted configuration state functions (CSFs) provide a compact many-electron basis for open-shell molecules. This basis is employed in one flavor of the recently introduced iterative configuration expansion (ICE) selected CI method. In this work, we implemented spin-dependent operators like spin-orbit coupling and direct spin-spin coupling for use in quasidegenerate perturbation theory on top of nonrelativistic/scalar-relativistic ICE wave functions. At the core of the new implementation are matrix elements of spin tensor excitation operators between CSFs, which are evaluated as products of orbital-specific factors. Two applications, the electron paramagnetic resonance g-factors of a MoIII-based catalytic intermediate and the zero-field splitting in dioxygen, illustrate the capabilities of the new method.