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• W2988690634 abstract "High-resolution velocity map imaged photoelectron spectra of the nitrite anion NO2– are measured over a range of photodetachment wavelengths between 355 and 550 nm, resolving the vibrational and rotational structure of the NO2(X̃2A1) + e– ← NO2–(X̃1A1) + hν transition. A full rotational band model is constructed to define the spectroscopic constants of both the neutral and the lesser studied anion ground states. The corresponding photoelectron angular distributions are characterized by a large positive anisotropy parameter, with β ≈ 1.5 gradually increasing to β ≈ 1.7 upon approaching the threshold. However, at very low kinetic energies, within 0.1 eV of the threshold, β dramatically drops to 0. This behavior is a consequence of the Wigner near-threshold selectivity of the electron partial-wave cross sections, whereby an atomic p-like orbital character adjacent to the threshold is favored. The full kinetic energy dependence of β is reproduced by a new mixed spd orbital model, yielding a NO2–(X̃1A1) molecular-orbital decomposition of 2% p, 44% s, and 54% d character." @default.
• W2988690634 created "2019-11-22" @default.
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• W2988690634 date "2019-11-11" @default.
• W2988690634 modified "2023-09-24" @default.
• W2988690634 title "Wigner Near-Threshold Effects in the Photoelectron Angular Distribution of NO₂^–" @default.
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• W2988690634 doi "https://doi.org/10.1021/acs.jpca.9b09073" @default.
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