Electron-Induced Synthesis of Formamide in Condensed Mixtures of Carbon Monoxide and Ammonia

Bredehöft, Jan Hendrik; Böhler, Esther; Schmidt, Fabian; Borrmann, Tobias; Swiderek, Petra

doi:10.1021/acsearthspacechem.6b00011

Cited by 25 publications

(52 citation statements)

References 38 publications

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“…In ideal cases, the products can even incorporate all atoms of the initial reactants [16]. As prototypical examples, the syntheses of ethylamine (CH 2 H 5 NH 2 ) from ethylene (C 2 H 4 ) and ammonia (NH 3 ) [17], ethanol (C 2 H 5 OH) from ethylene (C 2 H 4 ) and water (H 2 O) [18], as well as formamide (H 2 NCHO) from carbon monoxide (CO) and ammonia (NH 3 ) [19] have been observed under low-energy electron irradiation in cryogenic condensed ices cona e-mail: swiderek@uni-bremen.de (corresponding author) taining the starting compounds. It was proposed in all three cases that electron ionization (EI) of one of the reactants creates an attractive force between adjacent molecules.…”

Section: Introductionmentioning

confidence: 99%

Molecular synthesis in ices triggered by dissociative electron attachment to carbon monoxide

et al. 2021

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Chemical reactions in mixed molecular ices as relevant in the context of astrochemistry can be initiated by electron-molecule interactions. Dissociative electron attachment (DEA) as initiating step is identified from the enhancement of product yields upon irradiation at particular electron energies. Herein, we show that DEA to CO leads to the formation of HCN in mixed CO/$$\hbox {NH}_{{3}}$$ NH 3 ice at electron energies around 11 eV and 16 eV. We propose that this reaction proceeds via insertion of the neutral C fragment into a N–H bond. In the case of CO/$$\hbox {H}_{{2}}$$ H 2 O and CO/$$\hbox {CH}_{{3}}$$ CH 3 OH ices, a resonant enhancement of the yields of HCOOH and $$\hbox {CH}_{{3}}$$ CH 3 OCHO, respectively, is observed around 10 eV. In both ices, both molecular constituents exhibit DEA processes in this energy range so that the energy-dependent product yield alone does not uniquely identify the relevant DEA channel. However, we demonstrate by comparing with earlier results on mixed ices where CO is replaced by $$\hbox {C}_{{2}}\hbox {H}_{{4}}$$ C 2 H 4 that DEA to CO is again responsible for the enhanced product formation. In this case, $$\hbox {O}^{\cdot -}$$ O · - activates $$\hbox {H}_{{2}}$$ H 2 O or $$\hbox {CH}_{{3}}$$ CH 3 OH which leads to the formation of larger products. We thus show that DEA to CO plays an important role in electron-induced syntheses in molecular ices. Graphical abstract

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Section: Introductionmentioning

confidence: 99%

Molecular synthesis in ices triggered by dissociative electron attachment to carbon monoxide

et al. 2021

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“…The production of formamide present in mixed multilayer films of CO and NH 3 . The resonance like feature (red line) between 6 and 12 eV is characteristic of the synthesis of formamide by reactants prepared in a DEA process, Bredehöft et al [71].…”

Section: Electron Energy [Ev]mentioning

confidence: 98%

“…The ice was prepared with a mixing ratio of 1:8 and thickness corresponding to 12-18 monolayers and an electron exposure of 200 µC/cm 2 . Formamide is readily formed and the resonance like feature between 6 and 12 eV is characteristic of the synthesis by reactants prepared in a dissociative electron attachment process [71]. Similar experiments have shown that as many as 15 products can be formed by electron irradiation of pure methanol ices [72] including ethylene glycol and methyl formate whilst formamide HCONH 2 is formed in irradiation of binary mixtures of ammonia and methanol ice and the simplest amino acid glycine from irradiation of a methylamine and carbon dioxide ice [73].…”

Section: Possibility Of Electron Induced Surface Chemistrymentioning

confidence: 99%

“…process but electron induced chemistry within ices has been shown to be an efficient route to molecular synthesis and simple electron irradiation of primary ices has been shown to be produce most (all) of the larger molecular species. For example, Figure 6 shows the yield of formamide in an ice film composed of CO and NH3 as a function of electron energy [71]. The ice was prepared with a mixing ratio of 1:8 and thickness corresponding to 12-18 monolayers and an electron exposure of 200 μC/cm 2 .…”

Section: Possibility Of Electron Induced Surface Chemistrymentioning

confidence: 99%

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Rosetta Mission: Electron Scattering Cross Sections—Data Needs and Coverage in BEAMDB Database

Marinković

Bredehöft

Vujčić

et al. 2017

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Abstract:The emission of [O I] lines in the coma of Comet 67P/Churyumov-Gerasimenko during the Rosetta mission have been explained by electron impact dissociation of water rather than the process of photodissociation. This is the direct evidence for the role of electron induced processing has been seen on such a body. Analysis of other emission features is handicapped by a lack of detailed knowledge of electron impact cross sections which highlights the need for a broad range of electron scattering data from the molecular systems detected on the comet. In this paper, we present an overview of the needs for electron scattering data relevant for the understanding of observations in coma, the tenuous atmosphere and on the surface of 67P/Churyumov-Gerasimenko during the Rosetta mission. The relevant observations for elucidating the role of electrons come from optical spectra, particle analysis using the ion and electron sensors and mass spectrometry measurements. To model these processes electron impact data should be collated and reviewed in an electron scattering database and an example is given in the BEAMD, which is a part of a larger consortium of Virtual Atomic and Molecular Data Centre-VAMDC.

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“…cleavage of molecular bonds as well as possible molecular rearrangement and formation of new molecular bonds) of the involved molecular species. For example, the electron-induced synthesis of FA in an icy mixture of CO and was proposed via electron attachment as well as electron ionization [ 12 ]. Moreover, FA and its analogues, containing the amide bond, a key biochemical structure, serve as model systems to understand the role of low-energy electrons in radiation damage to the cellular compounds [ 13 , 14 ].…”

Section: Introductionmentioning

confidence: 99%

Electron ionization of clusters containing the formamide molecule

et al. 2021

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Studies on electron interactions with formamide (FA) clusters promote scientific interest as a model system to understand phenomena relevant to astrophysical, prebiotic, and radiobiological processes. In this work, mass spectrometric detection of cationic species for both small bare and microhydrated formamide clusters was performed at an electron ionization of 70 eV. Furthermore, a comparative analysis of the cluster spectra with the literature-reported gas-phase spectra is presented and discussed, revealing different reaction channels affected by the cluster environment. This study is essential in developing our understanding of both low-energy electron phenomena in clusters that can bridge the complexity gap between gas and realistic systems and the effect of hydration on electron-induced processes.

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Electron-Induced Synthesis of Formamide in Condensed Mixtures of Carbon Monoxide and Ammonia

Cited by 25 publications

References 38 publications

Molecular synthesis in ices triggered by dissociative electron attachment to carbon monoxide

Molecular synthesis in ices triggered by dissociative electron attachment to carbon monoxide

Rosetta Mission: Electron Scattering Cross Sections—Data Needs and Coverage in BEAMDB Database

Electron ionization of clusters containing the formamide molecule

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