title: Communication: existence of the doubly excited state that mediates the photoionization of azulene.
abstract: We use the high-level electronic structure computations based on the equation-of-motion coupled-cluster (EOMCC) theory to show that the previously postulated [V. Blanchet et al., J. Chem. Phys. 128, 164318 (2008)] doubly excited state of azulene, located below the ionization threshold and mediating the 1 + 2' multi-photon ionization that leads to a Rydberg fingerprint, exists. This supports the crucial role of doubly excited states in the Rydberg fingerprint spectroscopy, while demonstrating the usefulness of EOMCC methods in capturing such states.
authors.affiliation: Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA. piecuch@chemistry.msu.edu
authors.forename: Piotr
authors.initials: P
authors.lastname: Piecuch
authors.forename: Jared A
authors.initials: JA
authors.lastname: Hansen
authors.forename: David
authors.initials: D
authors.lastname: Staedter
authors.forename: Stéphane
authors.initials: S
authors.lastname: Faure
authors.forename: Valérie
authors.initials: V
authors.lastname: Blanchet
mesh_terms: D052176:Azulenes / Q000737:chemistry*; D055668:Photochemical Processes; D011789:Quantum Theory
chemical_list: D052176:Azulenes; C005525:azulene