Autoionization from the plasmon resonance in isolated 1-cyanonaphthalene

Bull, James N. ORCID:, Bolognesi, Paola, Anstöter, Cate S., Ashworth, Eleanor K., Navarro Navarrete, José E., Zhu, Boxing, Richter, Robert, Pal, Nitish, Chiarinelli, Jacopo, Avaldi, Lorenzo, Zettergren, Henning and Stockett, Mark H. (2023) Autoionization from the plasmon resonance in isolated 1-cyanonaphthalene. The Journal of Chemical Physics, 158 (24). ISSN 0021-9606

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Polycyclic aromatic hydrocarbons have widely been conjectured to be ubiquitous in space, as supported by the recent discovery of two isomers of cyanonaphthalene, indene, and 2-cyanoindene in the Taurus molecular cloud-1 using radioastronomy. Here, the photoionization dynamics of 1-cyanonaphthalene (1-CNN) are investigated using synchrotron radiation over the hν = 9.0–19.5 eV range, revealing that prompt autoionization from the plasmon resonance dominates the photophysics for hν = 11.5–16.0 eV. Minimal photo-induced dissociation, whether originating from an excited state impulsive bond rupture or through internal conversion followed by a statistical bond cleavage process, occurs over the microsecond timescale (as limited by the experimental setup). The direct photoionization cross section and photoelectron angular distributions are simulated using an ezDyson model combining Dyson orbitals with Coulomb wave photoejection. When considering these data in conjunction with recent radiative cooling measurements on 1-CNN+, which showed that cations formed with up to 5 eV of internal energy efficiently stabilize through recurrent fluorescence, we conclude that the organic backbone of 1-CNN is resilient to photodestruction by VUV and soft XUV radiation. These dynamics may prove to be a common feature for the survival of small polycyclic aromatic hydrocarbons in space, provided that the cations have a suitable electronic structure to support recurrent fluorescence.

Item Type: Article
Additional Information: Funding was provided by the Swedish Foundation for International Cooperation in Research and Higher Education (STINT) Grant for Internationalization program (Grant No. PT2017-7328 to M.H.S. and J.N.B.) and an EPSRC New Investigator Award (Grant No. EP/W018691 to JNB). E.K.A. acknowledges the University of East Anglia for a doctoral studentship. The work was supported by the MAECI Italy-Sweden project “Novel molecular tools for the exploration of the nanoworld” and the PRIN Grant No. 20173B72NB project “Predicting and controlling the fate of bio-molecules driven by extreme-ultraviolet radiation.” H.Z. acknowledges the Swedish Research Council for an individual project grant (Contract No. 2020-03437). This article is based upon work from COST Action CA18212—Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology). Electronic structure calculations were carried out on the High Performance Computing Cluster supported by the Research and Specialist Computing Support service at the University of East Anglia. Part of the theoretical work used resources from the iOpenShell Center for Computational Studies of Electronic Structure and Spectroscopy of Open-Shell and Electronically Excited Species (
Uncontrolled Keywords: physics and astronomy(all),physical and theoretical chemistry ,/dk/atira/pure/subjectarea/asjc/3100
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Faculty of Science > Research Groups > Chemistry of Light and Energy
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Depositing User: LivePure Connector
Date Deposited: 29 Jun 2023 09:32
Last Modified: 19 Jul 2023 08:30
DOI: 10.1063/5.0153058

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