Exact decoupling of the Dirac Hamiltonian. III. Molecular properties

Recent advances in the theory of the infinite-order Douglas-Kroll-Hess (DKH) transformation of the Dirac Hamiltonian require a fresh and unified view on the calculation of atomic and molecular properties. It is carefully investigated how the four-component Dirac Hamiltonian in the presence of arbitrary electric and magnetic potentials is decoupled to two-component form. In order to cover the whole range of electromagnetic properties on the same footing, a consistent description within the DKH theory is presented. Subtle distinctions are needed between errors arising from any finite-order DKH scheme and effects due to oversimplified and thus approximate decoupling strategies for the Dirac operator, which will, though being numerically negligible in most cases, still be visible in the infinite-order limit of the two-component treatment. Special focus is given to the issue, whether the unitary DKH transformations to be applied to the Dirac Hamiltonian should depend on the property under investigation or not. It is explicitly shown that up to third order in the external potential the transformed property operator is independent of the chosen parametrization of the unitary transformations of the generalized DKH scheme. Since the standard DKH protocol covers the transformation of one-electron integrals only, the presentation is developed for one-electron properties for the sake of brevity. Nevertheless, all findings for the calculation of one-electron properties within a two-component framework presented here also hold for two-electron properties as well.