The negative ion chemistry of nitric oxide in the gas phase

Chacko, Silvi A.; Wenthold, Paul G.

doi:10.1002/mas.20060

Cited by 22 publications

(14 citation statements)

References 118 publications

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“…The addition reaction that occurs with 3p is consistent with what is expected for the closed-shell, imide anion . In contrast, the N–O exchange reaction has been observed previously with nitrene radical anions and is interpreted as indicating an open-shell electronic structure . Consequently, our previous study indicates that while 3p has a robust ground-state singlet, 2p is either a ground-state triplet or a singlet with a thermally accessible triplet state …”

Section: Introductionsupporting

confidence: 87%

“…56 In contrast, the N−O exchange reaction has been observed previously with nitrene radical anions 57 and is interpreted as indicating an open-shell electronic structure. 58 Consequently, our previous study indicates that while 3p has a robust ground-state singlet, 2p is either a ground-state triplet or a singlet with a thermally accessible triplet state. 55 A low-lying triplet state for 2p is somewhat surprising considering that it is isoelectronic with p-benzoquinone, 1p, which is a singlet with a large (>2 eV) singlet−triplet splitting.…”

Section: ■ Introductionmentioning

confidence: 96%

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Photoelectron Spectroscopy Study of Quinonimides

et al. 2017

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Structures and energetics of o-, m-, and p-quinonimide anions (OCHN) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, and it is shown that accurate predictions for the electronic structure of the para-quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.

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Section: Introductionsupporting

confidence: 87%

Section: ■ Introductionmentioning

confidence: 96%

Photoelectron Spectroscopy Study of Quinonimides

et al. 2017

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“…With closed-shell anions, it can react as an electrophile, and addition is commonly observed. 59,60 However, because it is also a free radical with a very low electron affinity, 61 it is able to undergo radical reactions without competing electron transfer, and often exhibits characteristic reactivity with open-shell anions. 62−67 For example, phenylnitrene radical anions, including PN −68 and even the methylphenylnitrene [M−N 2 ] − radical anions formed in this work, react with NO by nitrogen−oxygen exchange to form the corresponding phenoxides.…”

Section: ■ Discussionmentioning

confidence: 99%

Anionic Substituent Control of the Electronic Structure of Aromatic Nitrenes

2013

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The electronic structures of phenylnitrenes with anionic π-donating substituents are investigated by using mass spectrometry and electronic structure calculations. Reactions of para-CH(2)(-)-substituted phenylnitrene, formed by dissociative deprotonation of p-azidotoluene, with CS(2) and NO indicate that it has a closed-shell singlet ground state, whereas reactions of p-oxidophenylnitrene formed by dissociative deprotonation of p-azidophenol indicate either a triplet ground state or a singlet with a small singlet-triplet splitting. The ground electronic state assignments based on ion reactivity are consistent with electronic structure calculations. The stability of the closed-shell singlet states in nitrenes is shown by Natural Resonance Theory to be very sensitive to the amount of deprotonated-imine character in the wave function, such that large changes in state energies can be achieved by small modifications of the electronic structure.

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“…2 , Bowen and co-workers [16,17] (see also their recent work [18] and the review [19] by Chacko and Wenthold) concluded that the trinitrogen dioxide anion admits several isomeric forms. Before focusing on the latter issue that in fact, as we believe, leads to resolving the N 3 O À 2 paradigm, let us mention that the DPS can provide some insight into the structural and energetics motifs of a molecular anion and the dissociative states of the corresponding neutral species.…”

Section: Experimental Puzzlesmentioning

confidence: 99%

On the paradigm

Alijah

Kryachko

2007

Journal of Molecular Structure

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A survey of the existing experimental and theoretical data on the trinitrogen dioxide anion N 3 O À 2 that manifests a controversy as to the number of isomers and their chemical structures is presented. To resolve the controversy, new computational studies are performed at the MP2/aug-cc-pVTZ computational level. Two hitherto unknown isomers are predicted, one with singlet and one with triplet spin multiplicity. The singlet isomer, structurally characterized as N 2 AE [ONO] À , is the most stable among all known isomers and accounts for fragmentation patterns observed in the recent dissociative photodetachment experiments.

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The negative ion chemistry of nitric oxide in the gas phase

Cited by 22 publications

References 118 publications

Photoelectron Spectroscopy Study of Quinonimides

Photoelectron Spectroscopy Study of Quinonimides

Anionic Substituent Control of the Electronic Structure of Aromatic Nitrenes

On the paradigm

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