Communication: existence of the doubly excited state that mediates the photoionization of azulene.

Piotr Piecuch (1) , Jared A Hansen (1) , David Staedter (2) , Stéphane Faure (2) , Valérie Blanchet (2)

1 Department of Chemistry [Michigan]
2 Femto (LCAR)

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.

Domaines: Chimie-Physique [physics.chem-ph]; Sciences du Vivant [q-bio]

Piotr Piecuch, Jared A Hansen, David Staedter, Stéphane Faure, Valérie Blanchet. Communication: existence of the doubly excited state that mediates the photoionization of azulene.. Journal of Chemical Physics, 2013, 138 (20), pp.201102. ⟨10.1063/1.4808014⟩. ⟨hal-00904855⟩