A Quasirelativistic Two-component Density Functional and Hartree-Fock Program

Abstract

Abstract This work describes the implementation of an efficient two-component quasirelativistic density functional and Hartree-Fock program. The fact that the basis functions are real can be exploited if a special internal representation of operators and density matrices is used. This also leads to a considerable reduction of the effort in the closed shell case. While in most applications to open shell molecules, the noncollinear approach to define a relativistic spin density is preferable, the collinear approach finds its application in the calculation of magnetic anisotropy energies. Linear algebra steps in the SCF procedure have a higher relative weight compared to the nonrelativistic case, therefore some care was necessary to make them fast when parallelizing the code. The quasirelativistic Hamiltonians that have been implemented are the ´zeroth-order regular approximation´ (ZORA) Hamiltonian, the Douglas-Kroll-Hess Hamiltonian up to the sixth order, together with an accurate approximation to treat the picture change effect of the electron interaction, and effective core potential (ECP) matrix elements. Geometry gradients are available for the ZORA and ECP methods.