Excited states of ortho‐nitrobenzaldehyde as a challenging case for single‐ and multi‐reference electronic structure theory

Abstract

AbstractWe present a large set of vertical excitation calculations for the ortho‐nitrobenzaldehyde (oNBA) molecule, which exhibits a very challenging excited‐state electronic structure like other nitroaromatic compounds. The single‐reference methods produce mostly consistent results up to about 5.5 eV. By contrast, the CAS second‐order perturbation theory (CASPT2) results depend sensitively on the employed parameters. At the CAS self‐consistent field level, the energies of the bright states are strongly overestimated while doubly excited states appear too low and mix with these states. This mixing hampers the CASPT2 step, leading to inconsistent results. Only by increasing the number of states in the state‐averaging step to about 40—to cover all bright states embedded in the double excitations—and employing extended multistate CASPT2 could CASPT2 results consistent with experiment be obtained. We assign the four bands in the molecule's spectrum: The weakest band at 3.7 eV arises from the states, the second one at 4.4 eV from the () state, the shoulder at 5.2 eV from the () state, and the maximum at 5.7 eV from the () states. We also highlight the importance of modern wave function analysis techniques in elucidating the absorption spectrum of challenging molecules.