Infrared spectroscopy of the n-propyl and i-propyl radicals in solid para-hydrogen

Pullen, Gregory T.; Franke, Peter R.; Haupa, Karolina Anna; Lee, Yuan‐Pern; Douberly, Gary E.

doi:10.1016/j.jms.2019.07.001

Cited by 9 publications

(12 citation statements)

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“…The weakly interacting medium provides ideal conditions for sensitive spectroscopic detection of the reaction products. The advantages and limitations of this method for astrochemical studies have been discussed, and the technique was recently applied to study several H-atom-abstraction and H-atom-addition reactions. ,− …”

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confidence: 99%

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Non-energetic, Low-Temperature Formation of C_α-Glycyl Radical, a Potential Interstellar Precursor of Natural Amino Acids

Schneiker

Góbi

Joshi

et al. 2021

J. Phys. Chem. Lett.

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The reaction of H atoms with glycine was investigated at 3.1 K in para-H 2 , a quantum-solid host. The reaction was followed by IR spectroscopy, with the spectral analysis aided by quantum chemical computations. Comparison of the experimental IR spectrum with computed anharmonic frequencies and intensities proved that, regardless of the reactant glycine conformation, C α -glycyl radical is formed in an H-atom-abstraction process with great selectivity. The product of the second H-atom abstraction, iminoacetic acid, was also observed in a smaller amount. The C α -glycyl radical is sensitive to UV light and decomposes to iminoacetic acid and H atom upon 280 nm radiation. Since the reactive radical center is located on the C α -atom, it is suggested that natural α-amino acids can be formed from glycine via the C α -glycyl radical by non-energetic mechanisms in the solid phase of the interstellar medium.

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confidence: 99%

“…Generally, H atoms can react with an H-containing molecule in solid para -H 2 in either an H-abstraction or an H-addition reaction. Despite that a radical is formed from a closed-shell molecule, both types of reactions are usually favored thermodynamically due to the high-energy reactant H atom. − …”

mentioning

confidence: 99%

Non-energetic, Low-Temperature Formation of C_α-Glycyl Radical, a Potential Interstellar Precursor of Natural Amino Acids

Schneiker

Góbi

Joshi

et al. 2021

J. Phys. Chem. Lett.

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“…In the first set of experiments, H atoms were generated by the method described in the studies of Anderson as well as Lee and co-workers. − For this, a second leak valve and stainless steel capillary were used to introduce Cl 2 to the main chamber. The SO 2 / para -H 2 ratio was 1:5500.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…To generate SOS, we have applied H atom reactions in solid para -H 2 at 3.1 K. This method was established in the past decade by the groups of Anderson and Lee. It is taking advantage of the phenomenon of quantum diffusion that allows for the efficient movement of the H atoms through the matrix, facilitating H addition and abstraction reactions. − Earlier studies in para -H 2 reported the successful hydrogenation of polycyclic aromatic hydrocarbons (PAHs), − HONO, isoprene, propene, and pyrrole . Hydrogen abstraction from the isolated molecule by the H atoms could also be detected recently in the case of formamide, methyl formate, and acetamide. − As it was shown by these studies, even if a H addition or a H abstraction reaction has a substantial barrier, it can be fast enough at very low temperatures due to H atom tunneling to observe it on the laboratory time scale.…”

Section: Introductionmentioning

confidence: 97%

“…It is taking advantage of the phenomenon of quantum diffusion that allows for the efficient movement of the H atoms through the matrix, facilitating H addition and abstraction reactions. 113−116 Earlier studies in para-H 2 reported the successful hydrogenation of polycyclic aromatic hydrocarbons (PAHs), 117−120 HONO, 121 isoprene, 122 propene, 123 and pyrrole. 124 Hydrogen abstraction from the isolated molecule by the H atoms could also be detected recently in the case of formamide, methyl formate, and acetamide.…”

Section: Introductionmentioning

confidence: 99%

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Successive Hydrogenation of SO and SO₂ in Solid para-H₂: Formation of Elusive Small Oxoacids of Sulfur

Góbi

Csonka

Bazsó

et al. 2021

ACS Earth Space Chem.

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The small oxoacids of sulfur (SOS), H x SO y (x, y = 1, 2), are considered to be key reactive intermediates in organic synthesis, biochemical processes, and atmospheric chemistry. They play a major role in the chemistry of S-rich planets and are likely present in the interstellar medium (ISM). To shed light on the processes in the ISM, the reactions of SO2 and sulfur monoxide (SO) with H atoms were studied at 3.1 K in a para-H2 quantum-solid host. In the case of SO, the formation of both HOS and hydroxysulfinyl (HSO) was observed. Although hydroxidooxidosulfur (HOSO) is more favored thermodynamically, HSO2 is more readily formed from SO2 due to kinetic (tunneling) control. Regarding the doubly hydrogenated species, sulfoxylic acid (S(OH)2), sulfinic acid (HS(O)OH), and tentatively dihydrogen sulfone (H2SO2) were identified among the products by IR spectroscopy. HOS and H2SO2 were observed for the first time, while the present IR spectroscopic data can contribute to the identification of SOS in the atmosphere of celestial bodies, e.g., Venus, Europa, or Io.

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Infrared Spectra of (Z)- and (E)-^•C₂H₃C(CH₃)I Radicals Produced upon Photodissociation of (Z)- and (E)-(CH₂I)HC═C(CH₃)I in Solid para-Hydrogen

Haupa

Chen

et al. 2020

J. Phys. Chem. A

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Ozonolysis of isoprene to produce Criegee intermediates such as methyl vinyl ketone oxide (MVKO), C2H3C(CH3)OO, is an important process in atmospheric chemistry. MVKO was recently produced and identified in laboratories after photolysis of a gaseous mixture of 1,3-diiodo-but-2-ene, (CH2I)HCC(CH3)I, and O2, but the mechanism of its formation remains unexplored. We synthesized pure (Z)- and (E)-1,3-diiodo-but-2-ene and measured their distinct IR spectra. Upon irradiation at 280 nm of (Z)- and (E)-1,3-diiodo-but-2-ene in solid p-H2 at 3.3 K, the fission of the terminal CI bond yields (Z)- and (E)-3-iodo-but-2-en-1-yl [•C2H3C(CH3)I] radicals, respectively. These radicals were characterized with infrared absorption lines at 2962.4, 1423.8, 1265.3, 1120.9/1127.0, 921.4/922.3, and 792.5/791.7 cm–1, and 16 additional weaker lines for (Z)-•C2H3C(CH3)I and 1405.2, 1208.2, 1106.0/1103.9, 934.2/933.4, and 785.1/784.9 cm–1 and five additional weaker ones for (E)-•C2H3C(CH3)I. The assignments were derived according to behavior on secondary photolysis and comparison of the vibrational wavenumbers and the IR intensities of observed lines with those calculated with the B2PLYP-D3/aug-cc-pVTZ-pp method. These observations confirmed that only the terminal I atom, not the central one, was photodissociated at 280 nm and, in solid p-H2, the excess energy after photodissociation induced no change in conformation. These new spectra of •C2H3C(CH3)I radicals can provide valuable information for the understanding of the mechanism of formation of Criegee intermediate MVKO from the source reaction of photolysis of (CH2I)HCC(CH3)I in O2 in the laboratory.

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Infrared spectroscopy of the n-propyl and i-propyl radicals in solid para-hydrogen

Cited by 9 publications

References 125 publications

Non-energetic, Low-Temperature Formation of C_α-Glycyl Radical, a Potential Interstellar Precursor of Natural Amino Acids

Non-energetic, Low-Temperature Formation of C_α-Glycyl Radical, a Potential Interstellar Precursor of Natural Amino Acids

Successive Hydrogenation of SO and SO₂ in Solid para-H₂: Formation of Elusive Small Oxoacids of Sulfur

Infrared Spectra of (Z)- and (E)-^•C₂H₃C(CH₃)I Radicals Produced upon Photodissociation of (Z)- and (E)-(CH₂I)HC═C(CH₃)I in Solid para-Hydrogen

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Infrared spectroscopy of the n-propyl and i-propyl radicals in solid para-hydrogen

Cited by 9 publications

References 125 publications

Non-energetic, Low-Temperature Formation of Cα-Glycyl Radical, a Potential Interstellar Precursor of Natural Amino Acids

Non-energetic, Low-Temperature Formation of Cα-Glycyl Radical, a Potential Interstellar Precursor of Natural Amino Acids

Successive Hydrogenation of SO and SO2 in Solid para-H2: Formation of Elusive Small Oxoacids of Sulfur

Infrared Spectra of (Z)- and (E)-•C2H3C(CH3)I Radicals Produced upon Photodissociation of (Z)- and (E)-(CH2I)HC═C(CH3)I in Solid para-Hydrogen

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Non-energetic, Low-Temperature Formation of C_α-Glycyl Radical, a Potential Interstellar Precursor of Natural Amino Acids

Non-energetic, Low-Temperature Formation of C_α-Glycyl Radical, a Potential Interstellar Precursor of Natural Amino Acids

Successive Hydrogenation of SO and SO₂ in Solid para-H₂: Formation of Elusive Small Oxoacids of Sulfur

Infrared Spectra of (Z)- and (E)-^•C₂H₃C(CH₃)I Radicals Produced upon Photodissociation of (Z)- and (E)-(CH₂I)HC═C(CH₃)I in Solid para-Hydrogen