Structural rearrangement of the acrylonitrile (AN) cluster in the gas phase under VUV one-photon radiation explored by mass-selected infrared spectroscopy

Li, Yujian; Song, Wentao; Jiang, Ningjing; Zhang, Wei; Xie, Min; Hu, Yongjun

doi:10.1016/j.saa.2019.117620

Cited by 12 publications

(19 citation statements)

References 28 publications

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“…In this experiment, the molecular beam temperature is estimated as ca. 100–150 K, − , and the proportions of the three isomers are about 74.36, 25.64, and 0.00%, respectively. This may indicate that the most populated conformer of the neutral cluster is (CH 3 NO 2 -NH 3 )-I, which contains three intermolecular hydrogen bonds.…”

Section: Resultsmentioning

confidence: 99%

“…In the experimental spectrum (Figure a), a very broad feature appears from 2659 to 3082 cm –1 , and the other two main features appear at ∼3165, and ∼3296 cm –1 . These broad features may be caused by the excess energy that still remained in the cationic cluster after the neutral clusters were ionized by the VUV laser (118 nm) . The very broad band from 2659 to 3082 cm –1 is out of the typical CH stretching vibration region.…”

Section: Resultsmentioning

confidence: 99%

“…These broad features may be caused by the excess energy that still remained in the cationic cluster after the neutral clusters were ionized by the VUV laser (118 nm). 39 The very broad band from 2659 to 3082 cm −1 is out of the typical CH stretching vibration region. It is noted that IR vibration of H-bonded shared protons in cations is commonly observed with extremely broad bandwidth, which is caused by their high anharmonicities and hot bands.…”

Section: Resultsmentioning

confidence: 99%

“…IR spectra of neutral and cationic gas-phase clusters of CH 3 NO 2 -NH 3 were observed in this experiment. The detailed experimental setups have been described previously; − only a brief description is given here. Gas-phase CH 3 NO 2 -NH 3 clusters are generally produced in supersonic jet expansion. − The mixture of ammonia and helium (He) was used as the carrier gas, and the concentration of ammonia is 5%.…”

Section: Methodsmentioning

confidence: 99%

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Proton Transfer in Nitromethane–Ammonia Clusters under VUV Single-Photon Ionization Explored by Infrared Spectroscopy and Theoretical Calculations

et al. 2021

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It is known that the acidity and reactivity of the CH bond can be enhanced after ionization. Also, this property plays a pivotal role in proton transfer reaction and in the formation of new molecules. Herein, infrared spectroscopy and high-precision quantum chemical calculations are used to study the neutral and cationic clusters of nitromethane−ammonia (CH 3 NO 2 -NH 3 ). It is found that in the neutral cluster, CH 3 NO 2 and NH 3 are mainly bonded by three intermolecular hydrogen bonds, in which electrostatic contribution plays a major role. After vacuum ultraviolet (VUV) single-photon ionization of CH 3 NO 2 -NH 3 , the positive charge redistributes from the ionized nitrogen atom of NH 3 to the CH 3 NO 2 molecule immediately. Then, the proton of CH 3 NO 2 transfers to NH 3 to form a proton-transferred type structure CH 2 NO 2 -NH 4 + , without any effective energy barrier, due to the positive hyperconjugation of cationic nitromethane. A closed loop of positive charge transfer takes place in the CH 3 NO 2 -NH 3 cluster after VUV ionization. The present work demonstrates that both the proton transfer reaction and charge transfer process have occurred in the ionized CH 3 NO 2 -NH 3 cluster. Moreover, it is found that the proton transfer reaction is a result of the highly acidic CH bond caused by hyperconjugation between the σ (CH) bond and π orbital.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Proton Transfer in Nitromethane–Ammonia Clusters under VUV Single-Photon Ionization Explored by Infrared Spectroscopy and Theoretical Calculations

et al. 2021

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“…20 And our recent infrared spectroscopy results indicated that cationic acrylonitrile dimer and trimer could produce new molecules under the vacuum ultraviolet (VUV) single photoionization (SPI), which will provide an evidence that the prebiotic nitrogenous molecules could be produced by ion−molecule reactions in the special environment of outer space. 21 For methanol, there are some studies on the infrared spectroscopy and the hydrogen bonding interaction of its clusters or mixed clusters. Bernstein and coworkers studied the IR spectra of methanol clusters, and the results showed that the clusters larger than the dimer have a ring isomer with OH groups involved in hydrogen bonding.…”

Section: Introduction Acrylonitrile (A) [Ch 2 Chcnmentioning

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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Vibrational study of acrylonitrile dimer and acrylonitrile-water hydrogen-bonded complexes in solid neon supported by ab initio calculations

Soulard

Tremblay

2022

Journal of Molecular Structure

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Structural rearrangement of the acrylonitrile (AN) cluster in the gas phase under VUV one-photon radiation explored by mass-selected infrared spectroscopy

Cited by 12 publications

References 28 publications

Proton Transfer in Nitromethane–Ammonia Clusters under VUV Single-Photon Ionization Explored by Infrared Spectroscopy and Theoretical Calculations

Proton Transfer in Nitromethane–Ammonia Clusters under VUV Single-Photon Ionization Explored by Infrared Spectroscopy and Theoretical Calculations

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

Vibrational study of acrylonitrile dimer and acrylonitrile-water hydrogen-bonded complexes in solid neon supported by ab initio calculations

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Structural rearrangement of the acrylonitrile (AN) cluster in the gas phase under VUV one-photon radiation explored by mass-selected infrared spectroscopy

Cited by 12 publications

References 28 publications

Proton Transfer in Nitromethane–Ammonia Clusters under VUV Single-Photon Ionization Explored by Infrared Spectroscopy and Theoretical Calculations

Proton Transfer in Nitromethane–Ammonia Clusters under VUV Single-Photon Ionization Explored by Infrared Spectroscopy and Theoretical Calculations

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

Vibrational study of acrylonitrile dimer and acrylonitrile-water hydrogen-bonded complexes in solid neon supported by ab initio calculations

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