Infrared Photodissociation Spectra of Acrylonitrile Cluster Ions

Ichihashi, Masahiko; Sadanaga, Yasuhiro; Kondow, Tamotsu

doi:10.1021/jp982663x

Cited by 9 publications

(6 citation statements)

References 23 publications

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“…In contrast, the mass spectrum of acrylonitrile cluster cations, (AN) n + , shows no anomaly in intensity. This observation is consistent with the reported results that no intracluster polymerization takes place in the cluster cation. , …”

Section: Resultssupporting

confidence: 94%

“…This observation is consistent with the reported results that no intracluster polymerization takes place in the cluster cation. 6, 20 Comparing the TOF spectra for the different expansion conditions in Figure 2, we note that large clusters are prefer- entially formed in Ar gas rather than in He gas. This can be understood by higher cooling efficiency of Ar gas as a seed gas and suggests lower internal energy of the cluster anions generated in Ar; this may lead to smaller probability of fragmentation.…”

Section: Mass Spectramentioning

confidence: 94%

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Deposition of Acrylonitrile Cluster Ions on Solid Substrates: Thin Film Formation by Intracluster Polymerization Products

Yoshida

Sato

2006

J. Phys. Chem. B

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Cluster anions of acrylonitrile (AN), known to give intracluster anionic polymerization products, were deposited on solid substrates. The obtained films were examined by using infrared absorption spectroscopy, X-ray photoemission spectroscopy, and gel permeation chromatography with the aid of quantum chemical calculations. The acquired spectroscopic data are similar to those of polyacrylonitrile (PAN), while the normal polymerization of AN or reactions related to PAN seemed not to occur noticeably. On the contrary, the product analysis shows that most of the constituent molecules of the films are formed via cyclohexane-1,3,5-tricarbonitrile (CHTCN), a dominant product of the intracluster polymerization of AN, accompanied by fragmentation and dimerization.

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Section: Resultssupporting

confidence: 94%

Section: Mass Spectramentioning

confidence: 94%

Deposition of Acrylonitrile Cluster Ions on Solid Substrates: Thin Film Formation by Intracluster Polymerization Products

Yoshida

Sato

2006

J. Phys. Chem. B

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“…•+ (n = 3-10) [21]. Both isomers are considerably less stable than D1 and play no obvious role in the dissociation chemistry of the dimer ions.…”

Section: The Self-protonation Of Acrylonitrile In the Dimer Ions And mentioning

confidence: 99%

The acrylonitrile dimer ion: A study of its dissociation via self-catalysis, self-protonation and cyclization into the pyrimidine radical cation

Ervasti¹,

Jobst²,

Burgers³

et al. 2007

International Journal of Mass Spectrometry

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Large energy barriers prohibit the rearrangement of solitary acrylonitrile ions, CH 2 CHC N•+ , into their more stable hydrogen-shift isomers CH 2 C C NH•+ or CH CH-C NH •+ . This prompted us to examine if these isomerizations occur by self-catalysis in acrylonitrile dimer ions. Such ions, generated by chemical ionization experiments of acrylonitrile with an excess of carbon dioxide, undergo five dissociations in the s time frame, as witnessed by peaks at m/z 53, 54, 79, 80 and 105 in their metastable ion mass spectrum. Collision experiments on these product ions, deuterium labeling, and a detailed computational analysis using the CBS-QB3 model chemistry lead to the following conclusions: (i) the m/z 54 ions are ions CH 2 CHC NH + generated by self-protonation in ion-dipole stabilized hydrogen-bridged dimer ions [CH 2 CHC N· · ·H-C(C N)CH 2 ]•+ and [CH 2 CHC N· · ·H-C(H)C(H)C N]•+ ; the proton shifts in these ions are associated with a small reverse barrier; (ii) dissociation of the Hbridged ions into CH 2 C C NH•+ or CH CH-C NH •+ by self-catalysis is energetically feasible but kinetically improbable: experiment shows that the m/z 53 ions are CH 2 CHC N•+ ions, generated by back dissociation; (iii) the peaks at m/z 79, 80 and 105 correspond with the losses of HCN, C 2 H 2 and H• , respectively. The calculations indicate that these ions are generated from dimer ions that have adopted the (much more stable) covalently bound "head-to-tail" structure [CH 2 CHC N-C(H 2 )C(H)C N]•+ ; experiments indicate that the m/z 79 (C 5 H 5 N) and m/z 105 (C 6 H 6 N 2 ) ions have linear structures but the m/z 80 (C 4 H 4 N 2 ) ions consist of ionized pyrimidine in admixture with its stable pyrimidine-2-ylidene isomer. Acrylonitrile is a confirmed species in interstellar space and our study provides experimental and computational evidence that its dimer radical cation yields the ionized prebiotic pyrimidine molecule.

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“…Previously, there were many studies on acrylonitrile, − methanol, , or their clusters . For the acrylonitrile, many researches focused on whether pyridine can be formed from acrylonitrile or its clusters in interstellar space.…”

Section: Introductionmentioning

confidence: 99%

Conformational Landscapes and Infrared Spectra of Gas-phase Interstellar Molecular Clusters [(C₃H₃N)(CH₃OH)_n, n = 1–4]

et al. 2020

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Acrylonitrile (A) is one of the important interstellar molecules, which is considered closely related to the origin of life. And methanol (M) is one of the commonly used solvents, which is also found in outer space. Herein, we obtained the infrared (IR) spectra of size-selected AM n (n = 1–4) clusters in supersonic jet by monitoring their fragments of H+AM n–1 (n = 1–4) with vacuum ultraviolet single-photon soft ionization/IR-depletion technique. IR spectra of AM n (n = 1–4) clusters were recorded in the CH and OH vibration bands in the range of 2700–3800 cm–1. Spectra of AM n (n = 1–4) clusters are similar in the CH stretching regions, while those show significant variations in the OH stretching regions with the increase of methanol molecules. Calculated IR spectra, which were predicted with the B3LYP-D3(BJ)/aug-cc-pVDZ method, were employed to compare with the experimental results. For AM, AM2, and AM3, the structures with the methanol cyclic hydrogen bonded with [N1–C4(H6)] of acrylonitrile are more stable than the other H-bonded structures. For the most stable structures of AM4, however, the results show that the acrylonitrile is binding to a H-bonded ring formed by OH groups of four methanol molecules. The AM, AM2, and AM3 conformers with the single ring on the C 1 side of acrylonitrile, such as C 1-AM-a, C 1-AM2-a, and C 1-AM3-a, are dominant in the gas phase, while the C 2-AM4-a conformer with the H-bonded ring formed by the OH groups on the C 2 side of acrylonitrile is more stable than that of CM4-A-a in our experimental conditions (>130 K). These findings may provide valuable insight into the microsolvation process of the interstellar molecules and other biomolecules in gas phase.

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Infrared Photodissociation Spectra of Acrylonitrile Cluster Ions

Cited by 9 publications

References 23 publications

Deposition of Acrylonitrile Cluster Ions on Solid Substrates: Thin Film Formation by Intracluster Polymerization Products

Deposition of Acrylonitrile Cluster Ions on Solid Substrates: Thin Film Formation by Intracluster Polymerization Products

The acrylonitrile dimer ion: A study of its dissociation via self-catalysis, self-protonation and cyclization into the pyrimidine radical cation

Conformational Landscapes and Infrared Spectra of Gas-phase Interstellar Molecular Clusters [(C₃H₃N)(CH₃OH)_n, n = 1–4]

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Infrared Photodissociation Spectra of Acrylonitrile Cluster Ions

Cited by 9 publications

References 23 publications

Deposition of Acrylonitrile Cluster Ions on Solid Substrates: Thin Film Formation by Intracluster Polymerization Products

Deposition of Acrylonitrile Cluster Ions on Solid Substrates: Thin Film Formation by Intracluster Polymerization Products

The acrylonitrile dimer ion: A study of its dissociation via self-catalysis, self-protonation and cyclization into the pyrimidine radical cation

Conformational Landscapes and Infrared Spectra of Gas-phase Interstellar Molecular Clusters [(C3H3N)(CH3OH)n, n = 1–4]

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Conformational Landscapes and Infrared Spectra of Gas-phase Interstellar Molecular Clusters [(C₃H₃N)(CH₃OH)_n, n = 1–4]