Excited-state Properties Beyond the Excitation Energy from Orbital-Optimized Density Functional Calculations II: Absorption Spectra

Abstract

Absorption spectra up to 10 eV are calculated for a set of small molecules using a variational density functional approach in which the orbitals are optimized for each excited state. A plane-wave basis set is employed to accurately describe diffuse Rydberg excitations, while the transition dipole moment is evaluated from nonorthogonal Kohn--Sham determinants within the projector augmented wave formalism. Comparison with higher-level coupled-cluster results shows that orbital-optimized calculations provide a good description of oscillator strengths for states with predominantly single-configurational character, even with the generalized gradient approximation functional PBE. The inclusion of exact exchange and self-interaction correction further improves the results, with the latter yielding the smallest errors (mean absolute relative error of $\sim$25%). In contrast, large errors for all functionals are found for multi-configurational states, due to an inability of the approach to describe the multi-configurational character. Instead, the nonorthogonality between the ground and excited states is not found to be a significant source of error. These results establish the performance of orbital-optimized density functional calculations for absorption spectra of small molecules and highlight the need for extensions that combine state-specific orbital relaxation with an explicit multi-configurational treatment.