Direct observation of the intermediate radical in the photodissociation of 1,3-cyclohexane dinitrite

Qin, Tai; Xue, Junfei; Huo, Dayujia; Zu, Lily

doi:10.1039/c9cp03895g

“…The most common methods are electric discharge, pyrolysis, and photolysis, used in many spectroscopic laboratories. [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 ] Nonetheless, these generation procedures typically require gaseous precursors prepared by mixing different gases or easily vaporizable liquids and solids. From this, solid organic compounds with high melting points and low vapor pressures are rarely utilized as potential precursors.…”

mentioning

confidence: 99%

An Innovative Approach for the Generation of Species of the Interstellar Medium

Kolesníková

¹

,

León

²

,

Alonso

³

et al. 2021

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The large amount of unstable species in the realm of interstellar chemistry drives an urgent need to develop efficient methods for the in situ generations of molecules that enable their spectroscopic characterizations. Such laboratory experiments are fundamental to decode the molecular universe by matching the interstellar and terrestrial spectra. We propose an approach based on laser ablation of nonvolatile solid organic precursors. The generated chemical species are cooled in a supersonic expansion and probed by high-resolution microwave spectroscopy. We present a proof of concept through a simultaneous formation of interstellar compounds and the first generation of aminocyanoacetylene using diaminomaleonitrile as a prototypical precursor. With this micro-laboratory, we open the door to generation of unsuspected species using precursors not typically accessible to traditional techniques such as electric discharge and pyrolysis.

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“…Therefore, dedicated laboratory experiments are needed to enable in situ generations. The most common methods are electric discharge, pyrolysis, and photolysis, used in many spectroscopic laboratories [7–20] . Nonetheless, these generation procedures typically require gaseous precursors prepared by mixing different gases or easily vaporizable liquids and solids.…”

Section: Figurementioning

confidence: 99%

“…The most common methods are electric discharge, pyrolysis, and photolysis, used in many spectroscopic laboratories. [7][8][9][10][11][12][13][14][15][16][17][18][19][20] Nonetheless, these generation procedures typically require gaseous precursors prepared by mixing different gases or easily vaporizable liquids and solids. From this, solid organic compounds with high melting points and low vapor pressures are rarely utilized as potential precursors.…”

mentioning

confidence: 99%

An Innovative Approach for the Generation of Species of the Interstellar Medium

Kolesníková

¹

,

León

²

,

Alonso

³

et al. 2021

Angewandte Chemie

3

0

View full text Add to dashboard Cite

The large amount of unstable species in the realm of interstellar chemistry drives an urgent need to develop efficient methods for the in situ generations of molecules that enable their spectroscopic characterizations. Such laboratory experiments are fundamental to decode the molecular universe by matching the interstellar and terrestrial spectra. We propose an approach based on laser ablation of nonvolatile solid organic precursors. The generated chemical species are cooled in a supersonic expansion and probed by high-resolution microwave spectroscopy. We present a proof of concept through a simultaneous formation of interstellar compounds and the first generation of aminocyanoacetylene using diaminomaleonitrile as a prototypical precursor. With this micro-laboratory, we open the door to generation of unsuspected species using precursors not typically accessible to traditional techniques such as electric discharge and pyrolysis.

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Structural effect on electron impact decomposition of 1,3- and 1,4-cyclohexane dinitrites

Qin

¹

,

Xue

²

,

Zu

³

2021

Chinese Journal of Chemical Physics

0

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Alkyl dinitrites have attracted attention as an important type of nitrosating agent and a pollution source in atmosphere. The reactivity and chemistry of alkyl dinitrites induced by the two ONO functional groups are relatively unknown. In this work, decompositions of 1,3- cyclohexane dinitrite and 1,4-cyclohexane dinitrite are studied by electron impact ionization mass spectroscopy (EI-MS). Apart from NO+ (m/z=30), fragment ions m/z=43 and 71 are the most abundant for the 1,3-isomer. On the other hand, fragments m/z=29, 57, 85, and 97 stand out in the EI-MS spectrum of 1,4-isomer. Possible dissociation mechanisms of the two dinitrites are proposed by theoretical calculations. The results reveal that the ring-opening of 1,3-cyclohexane dinitrite mainly starts from the intermediate ion (M-NO)+ by cleavage of two αC-βC bonds. For 1,4-cyclohexane dinitrite, in addition to the decomposition via intermediate (M-NO)+, cleavage of βC-βC bonds can occur directly from the parent cation M+. The results will help to understand the structural related chemistry of alkyl dinitrites in atmosphere and in NO transfer process.

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Direct observation of the intermediate radical in the photodissociation of 1,3-cyclohexane dinitrite

Abstract: The two-step photodissociation mechanism of 1,3-cyclohexane dinitrite is confirmed by observation of the laser-induced fluorescence spectrum of the intermediate 3-nitrosooxy cyclohexoxy radical.

Cited by 3 publications

References 38 publications

An Innovative Approach for the Generation of Species of the Interstellar Medium

An Innovative Approach for the Generation of Species of the Interstellar Medium

An Innovative Approach for the Generation of Species of the Interstellar Medium

Structural effect on electron impact decomposition of 1,3- and 1,4-cyclohexane dinitrites

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