Restricted open-shell time-dependent density functional theory with perturbative spin–orbit coupling

Abstract

When using quantum chemical methods to study electronically excited states of open-shell molecules, it is often beneficial to start with wave functions that are spin eigenfunctions. For excited states of molecules containing heavy elements, spin–orbit coupling (SOC) is important and needs to be included as well. An efficient approach is to include SOC perturbatively on top of a restricted open-shell Kohn–Sham (ROKS) time-dependent density functional theory, which can be combined with the Tamm–Dancoff approximation (TDA) to suppress numerical instabilities. We implemented and assessed the potential of such a ROKS-TDA-SOC method, also featuring the possibility of calculating transition dipole moments between states to allow for full spectrum simulation. Our study shows that the ROKS-TDA-SOC formalism yields a clear and easy-to-use method to obtain electronically excited states of open-shell molecules that are of moderate size and contain heavy elements.