Four-component relativistic time-dependent density-functional theory using a stable noncollinear DFT ansatz applicable to both closed- and open-shell systems.

We present a formulation of relativistic linear response time-dependent density functional theory for the calculation of electronic excitation energies in the framework of the four-component Dirac-Coulomb Hamiltonian. This approach is based on the noncollinear ansatz originally developed by Scalmani and Frisch [J. Chem. Theory Comput. 8, 2193 (2012)] and improves upon the past treatment of the limit cases in which the spin density approaches zero. As a result of these improvements, the presented approach is capable of treating both closed- and open-shell reference states. Robust convergence of the Davidson-Olsen eigenproblem algorithm for open-shell reference states was achieved through the use of a solver which considers both left and right eigenvectors. The applicability of the present methodology on both closed- and open-shell reference states is demonstrated on calculations of low-lying excitation energies for Group 3 atomic systems (Sc-Ac) with nondegenerate ground states, as well as for Group 11 atomic systems (Cu-Rg) and octahedral actinide complexes (PaCl , UCl , and NpF) with effective doublet ground states.