Ranković, Miloš and Nag, Pamir and Anstöter, Cate S. and Mensa-Bonsu, Golda and Kumar T. P., Ragesh and Verlet, Jan R. R. and Fedor, Juraj (2022) 'Resonances in nitrobenzene probed by the electron attachment to neutral and by the photodetachment from anion.', Journal of chemical physics., 157 (6). 064302.
We probe resonances (transient anions) in nitrobenzene with the focus on the electron emission from these. Experimentally, we populate resonances in two ways: either by the impact of free electrons on the neutral molecule or by the photoexcitation of the bound molecular anion. These two excitation means lead to transient anions in different initial geometries. In both cases, the anions decay by electron emission and we record the electron spectra. Several types of emission are recognized, differing by the way in which the resulting molecule is vibrationally excited. In the excitation of specific vibrational modes, distinctly different modes are visible in electron collision and photodetachment experiments. The unspecific vibrational excitation, which leads to the emission of thermal electrons following the internal vibrational redistribution, shows similar features in both experiments. A model for the thermal emission based on a detailed balance principle agrees with the experimental findings very well. Finally, a similar behavior in the two experiments is also observed for a third type of electron emission, the vibrational autodetachment, which yields electrons with constant final energies over a broad range of excitation energies. The entrance channels for the vibrational autodetachment are examined in detail, and they point to a new mechanism involving a reverse valence to non-valence internal conversion.
|Full text:||Publisher-imposed embargo until 08 August 2023. |
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|Publisher Web site:||https://doi.org/10.1063/5.0101358|
|Publisher statement:||This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Ranković, Miloš, Nag, Pamir, Anstöter, Cate S., Mensa-Bonsu, Golda, Kumar T. P., Ragesh, Verlet, Jan R. R. & Fedor, Juraj (2022). Resonances in nitrobenzene probed by the electron attachment to neutral and by the photodetachment from anion. The Journal of Chemical Physics 157(6): 064302 and may be found at https://doi.org/10.1063/5.0101358|
|Date accepted:||15 July 2022|
|Date deposited:||17 November 2022|
|Date of first online publication:||08 August 2022|
|Date first made open access:||08 August 2023|
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