The calculation of excitation energies based on the relativistic two-component zeroth-order regular approximation and time-dependent density-functional with full use of symmetry

Abstract

In the present work, we propose a relativistic time-dependent density-functional theory (TDDFT) based on the two-component zeroth-order regular approximation and a noncollinear exchange-correlation (XC) functional. This two-component TDDFT formalism has the correct nonrelativistic limit and affords the correct threefold degeneracy of triplet excitations. The relativistic TDDFT formalism is implemented into the AMSTERDAM DENSITY FUNCTIONAL program package for closed-shell systems with full use of double-group symmetry to reduce the computational effort and facilitate the assignments. The performance of the formalism is tested on some closed-shell atoms, ions, and a few diatomic molecules containing heavy elements. The results show that the fine structure of the excited states for most atoms and ions studied here can be accurately accounted for with a proper XC potential. For the excitation energies of the molecules studied here, the present formalism shows promise and the error encountered is comparable to that of nonrelativistic TDDFT calculations on light elements.