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), 10.1063/1.2913167] 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.
- Publication:
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Journal of Chemical Physics
- Pub Date:
- May 2013
- DOI:
- Bibcode:
- 2013JChPh.138t1102P
- Keywords:
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- coupled cluster calculations;
- molecule-photon collisions;
- multiphoton processes;
- organic compounds;
- photoionisation;
- Rydberg states;
- 33.80.Rv;
- 31.15.bw;
- 33.80.Eh;
- Multiphoton ionization and excitation to highly excited states;
- Clusters: electronic properties equilibrium geometries coupled-cluster theory;
- Autoionization photoionization and photodetachment