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Updated: Aug 19, 2025

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
Threshold Photoelectron Spectrum of m-Benzyne
M Gerlach1, E Karaev1, D Schaffner1
1Institute of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg, Germany.
Abstract:
Due to their unusual electronic structure, the biradical m-benzyne, C6H4, and its cation are of considerable interest in chemistry. Here, the photoion mass-selected threshold photoelectron spectrum of the m-benzyne biradical is presented. An adiabatic ionization energy of 8.65 ± 0.015 eV is derived, while a vibrational progression of 0.10 eV is assigned to the ν9+ ring breathing mode, in excellent agreement with computations. The experimental spectrum was reproduced well by Franck-Condon spectral modeling of the 2A1 ← X 1A1 transition, in which the cation retains a monocyclic C6 framework. The energetically close-lying bicyclic 2A2 cation state exhibits low Franck-Condon factors, due to the large change in geometry, and thus cannot be observed.
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