Photoelectron spectroscopy of the thiazate (NSO−) and thionitrite (SNO−) isomer anions

Lehman, Julia H.; Lineberger, W. C.

doi:10.1063/1.4984129

Cited by 5 publications

(3 citation statements)

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“…Experimentally, both 3a and 3b1 have been isolated and structurally characterized; 2,4,6,44 their photoelectron spectra have also been reported. 8,15 A comparison between computational and experimental structural data is, however, unwarranted due to crystallographic disorder in the positions of N and O atoms in the structures of 3a and 3b1.…”

Section: Here)mentioning

confidence: 99%

“…1 The similar values of all three vibrations for NSOsalts indicate only minor anion-cation interactions in the solid state; 5 consistently, a recent photoelectron spectroscopy study of NSOprovided values for the fundamental vibrations in good agreement with the IR data. 8 Although the NSOand NSN 2-anions have been employed in metathetical reactions to generate main group element and transition-metal complexes, 1,9 there have been relatively few computational studies of these fundamentally important species. An early investigation of the NSN 2-dianion by a combination of Hartree-Fock-Slater (HFS) and semi-empirical MNDO methods predicted two vastly different geometries, 10 whereas more recent computational work using MP2 and density functional theory (DFT) has reproduced the experimental geometry.…”

Section: Introductionmentioning

confidence: 99%

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Computational investigations of 18-electron triatomic sulfur–nitrogen anions

et al. 2018

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MRCI-SD/def2-QZVP and PBE0/def2-QZVP calculations have been employed for the analysis of geometries, stabilities, and bonding of isomers of the 18-electron anions N2S2−, NS2−, and NSO−. Isomers of the isoelectronic neutral molecules SO2, S2O, S3, and O3 are included for comparison. The sulfur-centered acyclic NSN2−, NSS−, and NSO− anions are the most stable isomers of their respective molecular compositions. However, the nitrogen-centered isomers SNS− and SNO− lie close enough in energy to their more stable counterparts to allow their occurrence. The experimental structural information, where available, is in good agreement with the optimized bond parameters. The bonding in all investigated species is qualitatively similar, though electron density analyses reveal important quantitative differences that arise from bond polarization. Most of the investigated systems can be described with a single configuration wave function, the two notable exceptions being isomers SSS and OOO that show some diradical character. The computed MRCI-SD/def2-QZVP absorption maxima for SNS− and NSS− are 342 and 327 nm, respectively. The corresponding PBE0/def2-QZVP values in acetonitrile are 353 and 333 nm. These data support the proposed initial formation of SNS− from electrochemical or chemical reduction of SSNS− based on experimental UV–vis spectra. The interconversion of SNS− and NSS− is calculated to be facile and reversible, leading to an equilibrium mixture that also includes the remarkably stable dianion SNSNSS2−. Thus, salts of either SNS− or NSS− with bulky organic cations represent feasible synthetic targets.

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Section: Here)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Computational investigations of 18-electron triatomic sulfur–nitrogen anions

et al. 2018

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“…Beyond the interest in the oxidation of isoprene via atmospheric chemical processes or in combustion, the speciation of molecular and complex ions generated in electrical discharges is of secondary interest from an experimental standpoint. Electrical discharges are well known to produce a variety of cationic, − anionic, − and neutral , products from simple hydrocarbons or other small molecules as starting materials, resulting in complex mass spectra. Many of these ions and their corresponding reactive neutrals may be present in interstellar medium. − Consequently, these species of potential astrochemical interest, and the methods by which they are formed, may inform experimental approaches to generating specific conformational isomers, as many interstellar species are otherwise difficult to reproduce in the laboratory setting.…”

Section: Introductionmentioning

confidence: 99%

Identification of Isoprene Oxidation Reaction Products via Anion Photoelectron Spectroscopy

2021

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We present a study on the oxidation of isoprene under several different conditions that may model both atmospheric and combustion chemistry. Anions, formed by passing isoprene/oxidant gas mixtures through a pulsed discharge generating a range of species, are separated via mass spectrometry and characterized by anion photoelectron (PE) spectroscopy supported by computations. Specifically, a UV-irradiated isoprene/O2 mixture, which additionally produces O3, and an isoprene/O2/H2 mixture, which generates •OH when passed through the discharge, were sampled. The mass spectra of ions generated under both conditions show the production of intact molecular ions, ion–molecule complexes (e.g., O2 –, O4 –, and O2 –·isoprene), and singly deprotonated species (e.g., deprotonated isoprene, C5H7 –). In addition, both smaller and oxidized fragments are observed using both gas mixtures, though relative abundances differ. From the UV-irradiated isoprene/O2 gas mixture, additional intact molecular products of reactions initiated by ozonolysis of isoprene, methylglyoxal, and dimethylglyoxal were observed. Fragmentation and oxidation of isoprene observed in both gas mixtures included species with m/z 39, 53, 67, 69, and 83 that we attribute to a series of alkyl- and alkenoxide-based anions. The coexistence of intact molecules and complexes with fragments and reaction products demonstrates the versatility of this ion source as a simple and efficient anion formation method for studying species that may be relevant in atmospheric and combustion chemistry.

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