Resonances in nitrobenzene probed by the electron attachment to neutral and by the photodetachment from anion

TY - JOUR

T1 - Resonances in nitrobenzene probed by the electron attachment to neutral and by the photodetachment from anion

AU - Ranković, Miloš

AU - Nag, Pamir

AU - Anstoter, Cate Sara

AU - Mensa-Bonsu, Golda

AU - Kumar T. P., Ragesh

AU - Verlet, Jan R. R.

AU - Fedor, Juraj

N1 - © 2022 Author(s). Published under an exclusive license by AIP Publishing. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

PY - 2022/8/8

Y1 - 2022/8/8

N2 - 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.

AB - 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.

U2 - 10.1063/5.0101358

DO - 10.1063/5.0101358

M3 - Article

SN - 0021-9606

VL - 157

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

M1 - 064302

ER -