Analytic energy gradients of spin-adapted open-shell time-dependent density functional theory.

Abstract

It is now well established that the spin-adapted time-dependent density functional theory [X-TD-DFT; Li and Liu, J. Chem. Phys. 135, 194106 (2011)] for low-lying excited states of open-shell systems has very much the same accuracy as the conventional TD-DFT for low-lying excited states of closed-shell systems. In particular, this has been achieved without computational overhead over the unrestricted TD-DFT (U-TD-DFT) that usually produces heavily spin-contaminated excited states. It is shown here that the analytic energy gradients of X-TD-DFT can be obtained by just slight modifications of those of U-TD-DFT running with restricted open-shell Kohn-Sham orbitals. As such, X-TD-DFT also has no overhead over U-TD-DFT in the calculation of energy gradients of excited states of open-shell systems. Although only a few prototypical open-shell molecules are considered as showcases, it can definitely be said that X-TD-DFT can replace U-TD-DFT for geometry optimization and dynamics simulation of excited states of open-shell systems.