Excited state geometries within time-dependent and restricted open-shell density functional theories

Abstract

Singlet excited state geometries of a set of medium sized molecules with different characteristic lowest excitations are studied. Geometry optimizations of excited states are performed with two closely related restricted open-shell Kohn-Sham methods and within linear response to time-dependent density functional theory. The results are compared to wave-function based methods. Excitation energies (vertical and adiabatic) calculated from the open-shell methods show systematic errors depending on the type of excitation. However, for all states accessible by the restricted methods a good agreement for the geometries with time-dependent density functional theory and wave-function based methods is found. An analysis of the energy with respect to the mixing angle for the singly occupied orbitals reveals that some states (mostly {[}n --> pi{*}]) are stable when symmetry constraints are relaxed and others (mostly [pi --> pi{*}]) are instable. This has major implications on the applicability of the restricted open-shell methods in molecular dynamics simulations.