Making four- and two-component relativistic density functional methods fully equivalent based on the idea of “from atoms to molecule”

Abstract

It is shown that four- and two-component relativistic Kohn-Sham methods of density functional theory can be made fully equivalent in all the aspects of simplicity, accuracy, and efficiency. In particular, this has been achieved based solely on physical arguments rather than on mathematical tricks. The central idea can be visualized as “from atoms to molecule,” reflecting that the atomic information is employed to “synthesize” the molecular no-pair relativistic Hamiltonian. That is, the molecular relativistic Hamiltonian can, without loss of accuracy, be projected onto the positive energy states of the isolated Dirac atoms with the projector approximated simply by the superposition of the atomic ones. The dimension of the four-component Hamiltonian matrix then becomes the same as that of a two-component one. Another essential ingredient is to formulate quasirelativistic theory on matrix form rather than on operator form. The resultant quasi-four-component, normalized elimination of the small component, and symmetrized elimination of the small component approaches are critically examined by taking the molecules of MH and M2 (M=At, E117) as examples.