The recent discovery of cyano-substituted aromatic and two-ring polycyclic aromatic hydrocarbon molecules in Taurus Molecular Cloud-1 has prompted questions on how the electronic structure and excited-state dynamics of these molecules are linked with their existence and abundance. Here, we report a photodetachment and frequency- and angle-resolved photoelectron spectroscopy study of jet-cooled para-deprotonated benzonitrile (p-[Bzn-H]−). The adiabatic detachment energy was determined as 1.70 ± 0.01 eV, in good agreement with CCSD(T)/aug-cc-pVTZ calculations. The spectra across the first few electron-volts above threshold are dominated by prompt autodetachment processes associated with excitation of at least five short-lived (tens of femtoseconds) temporary anion shaped resonances since excitation cross sections are several orders of magnitude larger than direct photodetachment cross sections. The photoexcitation vibronic profile is dominated by a ≈640 cm−1 ring deformation mode. [Bzn-H]− lacks a valence-localized excited state situated below the detachment threshold and does not exhibit thermionic emission following excitation of the temporary anion resonances. Thus, [Bzn-H]− is unlikely to be stable in many interstellar environments.
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21 September 2024
Research Article|
September 16 2024
Photoelectron spectroscopy of deprotonated benzonitrile
Eleanor K. Ashworth
;
Eleanor K. Ashworth
(Data curation, Formal analysis, Investigation, Writing – review & editing)
1
School of Chemistry, Norwich Research Park, University of East Anglia
, Norwich NR4 7TJ, United Kingdom
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James N. Bull
James N. Bull
a)
(Conceptualization, Formal analysis, Funding acquisition, Supervision, Writing – original draft, Writing – review & editing)
1
School of Chemistry, Norwich Research Park, University of East Anglia
, Norwich NR4 7TJ, United Kingdom
2
Centre for Photonics and Quantum Science, University of East Anglia
, Norwich NR4 7TJ, United Kingdom
a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 161, 114302 (2024)
Article history
Received:
July 29 2024
Accepted:
August 29 2024
Citation
Eleanor K. Ashworth, James N. Bull; Photoelectron spectroscopy of deprotonated benzonitrile. J. Chem. Phys. 21 September 2024; 161 (11): 114302. https://doi.org/10.1063/5.0231206
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