Zero field splitting of the chalcogen diatomics using relativistic correlated wave-function methods

The spectrum arising from the (π*)2 configuration of the chalcogen dimers, namely, the X21, a2, and b0+ states, is calculated using wave-function theory based methods. Two-component (2c) and four-component (4c) multireference configuration interaction (MRCI) and Fock-space coupled cluster (FSCC) methods are used as well as two-step methods spin-orbit complete active space perturbation theory at 2nd order (SO-CASPT2) and spin-orbit difference dedicated configuration interaction (SO-DDCI). The energy of the X21 state corresponds to the zero-field splitting of the ground state spin triplet. It is described with high accuracy by the 2- and 4-component methods in comparison with experiment, whereas the two-step methods give about 80% of the experimental values. The b0+ state is well described by 4c-MRCI, SO-CASPT2, and SO-DDCI, but FSCC fails to describe this state and an intermediate Hamiltonian FSCC ansatz is required. The results are readily rationalized by a two-parameter model; Δε, the π* spinor splitting by spin-orbit coupling and K, the exchange integral between the \documentclass[12pt]{minimal}\begin{document}$\pi _{1}^{*}$\end{document}π1* and the \documentclass[12pt]{minimal}\begin{document}$\pi _{-1}^{*}$\end{document}π−1* spinors with, respectively, angular momenta 1 and −1. This model holds for all systems under study with the exception of Po2.