Photochemistry of XCH<sub>2</sub>CN (X = −Cl, −SH) in Argon Matrices

Zapala, Joanna; Custer, Thomas; Guillemin, Jean‐Claude; Gronowski, Marcin

doi:10.1021/acs.jpca.9b01983

Cited by 3 publications

(9 citation statements)

References 105 publications

(189 reference statements)

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“…The C 2 H 5 SH sample was purchased from Sigma-Aldrich. The spectrophotometric equipment used here, consisting of a Bruker Vertex 70 FTIR spectrometer with 0.2 cm –1 resolution, a closed-cycle helium refrigerator (DE-202SE, Advanced Research Systems) and associated vacuum system, and vacuum manifold for mixture preparation, have been described previously . Matrices were prepared by starting from a degassed sample and then mixing with Ar (5.0 Multax s.c.) or CO (4.7 Praxair) at a molar ratio of 1:1000 (sample/Ar or CO).…”

Section: Experimental Methodsmentioning

confidence: 99%

“…The resulting luminescence spectra were recorded by a Mightex CCD spectrometer (HRS series, 300–1070 nm spectral range, 1.7 nm resolution). This method is helpful for the indirect detection of atomic sulfur because several emissions may appear, including: c 1 Σ – → a 1 Δ of SO, B″ 3 Π u → X 3 Σ g of S 2 ; B 3 Σ – u → X 3 Σ – g of S 2 , a 3 B 1 → X 1 A 1 of SO 2 and 3 Σ + → X 1 Σ + of OCS, and a 3 Π → X 1 Σ of carbon monosulfide (CS). − We previously used the same method to detect free sulfur produced during the photolysis of the mercaptoacetonitrile (HSCH 2 CN) …”

Section: Experimental Methodsmentioning

confidence: 99%

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UV Photolysis of C₂H₅SH in Solid CO and Ar

Purzycka

Custer

Gronowski

2021

ACS Earth Space Chem.

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Ethanethiol (C2H5SH) contains the −SH group, a functional group considered to be crucial for the prebiotic polymerization of amino acids. Ethanethiol is also one of about 250 molecules detected in the interstellar medium or circumstellar shells. We irradiated C2H5SH embedded in carbon monoxide (CO) as well as argon (Ar) ices. Using spectroscopy, we detected methane (CH4), ethane (C2H6), ethylene (C2H4), acetylene (C2H2), carbon monosulfide (CS), carbonyl sulfide (OCS), dihydrogen sulfide (SH2), thioformaldehyde (H2CS), ethanethial (CH3CHS), thiirane, ethenethione (H2CCS), ethynethiol (HCCSH), thiirene, ethenedithione (SCCS), methylene radical (CH2), ethylthiyl radical (C2H5S), thioketenyl radical (HCCS), sulfanyl radical (SH), and sulfur atoms. Additionally, we observed OCS luminescence during annealing of the Ar matrix sample, which indicates the existence of a free sulfur atom. All products contain fewer atoms than the parent. CH3CHS was the main organic product in CO; OCS is the only product detected that formed due to a reaction with CO. Quantum chemical computations show that the S–H bond can easily be broken upon electronic excitation. Although more experimental and theoretical data are needed, we suggest that C2H5SH can exist only in interstellar clouds shielded from UV radiation like G+0.693-0.027 but not in Orion KL.

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Section: Experimental Methodsmentioning

confidence: 99%

Section: Experimental Methodsmentioning

confidence: 99%

UV Photolysis of C₂H₅SH in Solid CO and Ar

Purzycka

Custer

Gronowski

2021

ACS Earth Space Chem.

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“…Note that, in the former reaction, iodine atoms bond directly to the carbonyl group only Fig. 7 Cryogenic photolysis of 2-sulfanylethanenitrile results in the formation of structural isomeric products (Zapała et al 2019) When similar experiments were used to investigate the photochemistry between CS 2 and the dihalides Cl 2 , Br 2 , and ClBr in a Ar ice matrix, both syn-and anti-halogenothiocarbonylsulfenyl halides based on X-C(=S)-S-Y backbones were detected (X and Y once again being the constituent atoms of the original dihalide), among other products (Fig. 6; Tobón et al 2007).…”

Section: Laboratory Photochemistry Experimentsmentioning

confidence: 99%

“…Solid phase photochemistry of more complex, exotic molecules may yield significant insights into the chemistry of different functional groups found in the interstellar medium. For instance, Zapała et al (2019) recently examined the photolysis of 2-sulfanylethanenitrile in a Ar matrix at 6 K. A related compound, sulfanylmethanenitrile, has already been detected in the interstellar medium (Halfen et al 2009). Their results showed that, among some photo-dissociation products formed via the loss of -CN and -SH groups, several isocyano compounds were produced as a result of photo-isomerisation processes (Zapała et al 2019; Fig.…”

Section: Laboratory Photochemistry Experimentsmentioning

confidence: 99%

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Sulfur Ice Astrochemistry: A Review of Laboratory Studies

et al. 2021

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Sulfur is the tenth most abundant element in the universe and is known to play a significant role in biological systems. Accordingly, in recent years there has been increased interest in the role of sulfur in astrochemical reactions and planetary geology and geochemistry. Among the many avenues of research currently being explored is the laboratory processing of astrophysical ice analogues. Such research involves the synthesis of an ice of specific morphology and chemical composition at temperatures and pressures relevant to a selected astrophysical setting (such as the interstellar medium or the surfaces of icy moons). Subsequent processing of the ice under conditions that simulate the selected astrophysical setting commonly involves radiolysis, photolysis, thermal processing, neutral-neutral fragment chemistry, or any combination of these, and has been the subject of several studies. The in-situ changes in ice morphology and chemistry occurring during such processing are often monitored via spectroscopic or spectrometric techniques. In this paper, we have reviewed the results of laboratory investigations concerned with sulfur chemistry in several astrophysical ice analogues. Specifically, we review (i) the spectroscopy of sulfur-containing astrochemical molecules in the condensed phase, (ii) atom and radical addition reactions, (iii) the thermal processing of sulfur-bearing ices, (iv) photochemical experiments, (v) the non-reactive charged particle radiolysis of sulfur-bearing ices, and (vi) sulfur ion bombardment of and implantation in ice analogues. Potential future studies in the field of solid phase sulfur astrochemistry are also discussed in the context of forthcoming space missions, such as the NASA James Webb Space Telescope and the ESA Jupiter Icy Moons Explorer mission.

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Energetic processing of thioacetamide in cryogenic matrices

Góbi,

Keresztes,

Schneiker

et al. 2024

The Journal of Chemical Physics

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There is an ongoing debate on the apparent depletion of sulfur in the interstellar medium (ISM) compared to its universal abundance; therefore, the investigation of sulfurous compounds at low temperatures is of utmost importance. This work aims to study thioacetamide, H3C–C(=S)–NH2, in low-temperature inert Ar and para-H2 matrices by IR spectroscopy. The samples have been exposed to various sources of irradiation, such as Lyman-α or laser UV photons as well as energetic electrons. Using different host materials enabled assessing the matrix’s impact on precursor decomposition. The response of the molecule to different types of irradiation has also been evaluated. The existence of three main decomposition channels were deduced: formation of (i) CH3, CH4, and HNCS; (ii) H2S and H2C=C=NH; and (iii) NH3 and H2C=C=S. The H3C–CN and H3C–NC isomers of H2C=C=NH could also be identified. Secondary products such as HNC and HCN were also detected in the quantum solid para-H2 in contrast to the more rigid Ar matrix. The listed decomposition products have been observed in the ISM, with the exception of H2C=C=NH and H3C–NC. The results point to the potential sensitivity of the precursor molecule to energetic radiation in space environments. Finally, the findings of this work will serve as a foundation for future irradiation experiments using the astrochemically more relevant pure thioacetamide ice.

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Photochemistry of XCH₂CN (X = −Cl, −SH) in Argon Matrices

Cited by 3 publications

References 105 publications

UV Photolysis of C₂H₅SH in Solid CO and Ar

UV Photolysis of C₂H₅SH in Solid CO and Ar

Sulfur Ice Astrochemistry: A Review of Laboratory Studies

Energetic processing of thioacetamide in cryogenic matrices

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Photochemistry of XCH2CN (X = −Cl, −SH) in Argon Matrices

Cited by 3 publications

References 105 publications

UV Photolysis of C2H5SH in Solid CO and Ar

UV Photolysis of C2H5SH in Solid CO and Ar

Sulfur Ice Astrochemistry: A Review of Laboratory Studies

Energetic processing of thioacetamide in cryogenic matrices

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Product

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Photochemistry of XCH₂CN (X = −Cl, −SH) in Argon Matrices

UV Photolysis of C₂H₅SH in Solid CO and Ar

UV Photolysis of C₂H₅SH in Solid CO and Ar