Efficient treatment of the Hartree interaction in the relativistic Kohn-Sham problem

We elaborate the two-component Douglas-Kroll reduction of the Dirac-Kohn-Sham problem of relativistic density-functional theory as introduced by Matveev and Rösch [J. Chem. Phys. 118, 3997 (2003)]. That method retains corrections to the Coulomb self-interaction (or Hartree) term of the energy functional that are due to the picture change. Using analytic expressions for the matrix elements, one is able to abandon the resolution of the identity approach for a crucial step of the relativistic transformation. Thus, a major source of uncertainties of the method is eliminated because basis sets no longer have to be extended by functions of higher angular momentum, previously required to ensure kinetic balance. This approach also relies on the electron charge-density fitting scheme via an auxiliary basis set. An efficient approximate implementation results if one restricts the relativistic transformation to the spherically symmetric atom-centered auxiliary functions. It provides accurate results while simplifying greatly the expressions for the matrix elements of the relativistically transformed operators and significantly reducing the computational effort. We demonstrate the performance of the method for the fine structure of one-electron levels of the Hg atom, the g -tensor shifts of N O2, and the properties of the diatomic molecules Bi2, Pb2, PbO, and TlH.