title: Semiempirical Quantum-Chemical Orthogonalization-Corrected Methods: Benchmarks of Electronically Excited States.
abstract: The semiempirical orthogonalization-corrected OMx methods have recently been shown to perform well in extensive ground-state benchmarks. They can also be applied to the computation of electronically excited states when combined with a suitable multireference configuration interaction (MRCI) treatment. We report on a comprehensive evaluation of the performance of the OMx/MRCI methods for electronically excited states. The present benchmarks cover vertical excitation energies, excited-state equilibrium geometries (including an analysis of significant changes between ground- and excited-state geometries), minimum-energy conical intersections, ground- and excited-state zero-point vibrational energies, and 0-0 transition energies for a total of 520 molecular structures and 412 excited states. For comparison, we evaluate the TDDFT/B3LYP method for all benchmark sets, and the CC2, MRCISD, and CASPT2 methods for some of them. We find that the current OMx/MRCI methods perform reasonably well for many of the excited-state properties. However, in comparison to the first-principles methods, there are also a number of shortcomings that should be addressed in future developments.
authors.affiliation: Max-Planck-Institut für Kohlenforschung , 45470 Mülheim an der Ruhr, Germany.
authors.forename: Deniz
authors.initials: D
authors.lastname: Tuna
authors.affiliation: Max-Planck-Institut für Kohlenforschung , 45470 Mülheim an der Ruhr, Germany.
authors.forename: You
authors.initials: Y
authors.lastname: Lu
authors.affiliation: Max-Planck-Institut für Kohlenforschung , 45470 Mülheim an der Ruhr, Germany.
authors.forename: Axel
authors.initials: A
authors.lastname: Koslowski
authors.affiliation: Max-Planck-Institut für Kohlenforschung , 45470 Mülheim an der Ruhr, Germany.
authors.forename: Walter
authors.initials: W
authors.lastname: Thiel