Resolution of identity Dirac-Kohn-Sham method using the large component only: Calculations of g-tensor and hyperfine tensor

摘要

A new relativistic two-component density functional approach, based on the Dirac-Kohn-Sham method and an extensive use of the technique of resolution of identity (RI), has been developed and is termed the DKS2-RI method. It has been applied to relativistic calculations of g and hyperfine tensors of coinage-metal atoms and some mercury complexes. The DKS2-RI method solves the Dirac-Kohn-Sham equations in a two-component framework using explicitly a basis for the large component only, but it retains all contributions coming from the small component. The DKS2-RI results converge to those of the four-component Dirac-Kohn-Sham with an increasing basis set since the error associated with the use of RI will approach zero. The RI approximation provides a basis for a very efficient implementation by avoiding problems associated with complicated integrals otherwise arising from the elimination of the small component. The approach has been implemented in an unrestricted noncollinear two-component density functional framework. DKS2-RI is related to Dyall's [J. Chem. Phys. 106, 9618 (1997)] unnormalized elimination of the small component method (which was formulated at the Hartree-Fock level and applied to one-electron systems only), but it takes advantage of the local Kohn-Sham exchange-correlation operators (as, e.g., arising from local or gradient-corrected functionals). The DKS2-RI method provides an attractive alternative to existing approximate two-component methods with transformed Hamiltonians (such as Douglas-Kroll-Hess [Ann. Phys. 82, 89 (1974); Phys. Rev. A 33, 3742 (1986)] method, zero-order regular approximation, or related approaches) for relativistic calculations of the structure and properties of heavy-atom systems. In particular, no picture-change effects arise in the property calculations.