Eliminating spin-contamination of spin-flip time dependent density functional theory within linear response formalism by the use of zeroth-order mixed- reference (MR) reduced density matrix

Abstract

The use of the mixed reference (MR) reduced density matrix, which combines reduced density matrices of the M-S = +1 and -1 triplet-ground states, is proposed in the context of the collinear spin-fliptime-dependent density functional theory (SF-IDDFT) methodology. The time-dependent Kohn-Sham equation with the mixed state is solved by the use of spinor-like open-shell orbitals within the linear response formalism, which enables to generate additional configurations in the realm of TD-DFT. The resulting MR-SF-TDDFT computational scheme has several advantages before the conventional collinear SF-IDDFT. The spin-contamination of the response states of SF-IDDFT is nearly removed. This considerably simplifies the identification of the excited states, especially in the "black-box" type applications, such as the automatic geometry optimization, reaction path following, or molecular dynamics simulations. With the new methodology, the accuracy of the description of the excited states is improved as compared to the collinear SF-IDDFT. Several test examples, which include systems typified by strong non-dynamic correlation, orbital (near) degeneracy, and conical intersections, are given to illustrate the performance of the new method.