Quantum Tunneling Mediated Low-Temperature Synthesis of Interstellar Hemiacetals

Wang, Jia; Nikolayev, Anatoliy A.; Marks, Joshua H.; Mcanally, Mason; Azyazov, Valeriy N.; Eckhardt, André K.; Mebel, Alexander M.; Kaiser, Ralf I.

doi:10.1021/acs.jpclett.3c01144

Cited by 7 publications

(3 citation statements)

References 41 publications

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“…The presence of electron-withdrawing groups such as hydroxyl (−OH) in a molecule has a strong tendency to promote dissociation in radical cations driven by the thermodynamically favorable separation of a radical and cation. , It is therefore vital to anticipate potential dissociative channels of the radical cations through computational quantum chemical assessment of methanetriol ( 1 •+ ), hydroxyperoxymethane ( 2 •+ ), and hydroperoxyl-methanol ( 3 •+ ). Gas-phase calculations carried out at the CCSD(T)/CBS//ωB97X-D/aug-cc-pVTZ level of theory identify three neutral structural isomers 1 – 3 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…In the blank (unirradiated) experiment, only the methanol cation (CH 3 OH + ) was detected. Since organic species featuring substitution by electron-withdrawing substituents such as hydroxyl groups on the same carbon atom are unstable as radical cations and face a small barrier to dissociation yielding a radical and a closed-shell cation, , the aforementioned electronic structure calculations provide the only vital way to assess the ionization energies and thus to guide the selection of the photon energies for the photoionization in the experiment. − …”

Section: Resultsmentioning

confidence: 99%

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Methanetriol─Formation of an Impossible Molecule

Marks,

Bai,

Nikolayev

et al. 2024

J. Am. Chem. Soc.

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Orthocarboxylic acids�organic molecules carrying three hydroxyl groups at the same carbon atom�have been distinguished as vital reactive intermediates by the atmospheric science and physical (organic) chemistry communities as transients in the atmospheric aerosol cycle. Predicted short lifetimes and their tendency to dehydrate to a carboxylic acid, free orthocarboxylic acids, signify one of the most elusive classes of organic reactive intermediates, with even the simplest representative methanetriol (CH(OH) 3 )�historically known as orthoformic acid�not previously been detected experimentally. Here, we report the first synthesis of the previously elusive methanetriol molecule in low-temperature mixed methanol (CH 3 OH) and molecular oxygen (O 2 ) ices subjected to energetic irradiation. Supported by electronic structure calculations, methanetriol was identified in the gas phase upon sublimation via isomerselective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies and the detection of photoionization fragments. The first synthesis and detection of methanetriol (CH(OH) 3 ) reveals its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition. These findings progress our fundamental understanding of the chemistry and chemical bonding of methanetriol, hydroxyperoxymethane (CH 3 OOOH), and hydroxyperoxymethanol (CH 2 (OH)OOH), which are all prototype molecules in the oxidation chemistry of the atmosphere.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Methanetriol─Formation of an Impossible Molecule

Marks,

Bai,

Nikolayev

et al. 2024

J. Am. Chem. Soc.

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“…Previous work by Song et al ( 3 ) revealed that reaction is exoergic by 22 kJ mol −1 with an entrance barrier of 106 kJ mol −1 (1.1 eV) calculated at the MRCISD+Q/cc-pVTZ//CASSCF/cc-pVTZ level of theory ( 44 ). Note that gas-phase calculations may overestimate the real barrier of the reactions because nearby molecules in the ice phase could be involved in the reaction mechanism ( 45 , 46 ). Furthermore, the suprathermal hydrogen atoms have excess kinetic energy of a few electron volts ( 47 ); this energy can be used to overcome the entrance barrier of reaction (3), leading eventually to 11 ( 35 ) as identified through FTIR spectroscopy at 1849 cm −1 for 11 (ν 2 ; HOĊO) in irradiated CO 2 −HOCH 2 CH 2 OH ice and at 1811 cm −1 for 11- 13 C (ν 2 ; HO 13 ĊO) in irradiated 13 CO 2 −HO 13 CH 2 13 CH 2 OH ice.…”

Section: Resultsmentioning

confidence: 99%

Interstellar formation of glyceric acid [HOCH ₂ CH(OH)COOH]—The simplest sugar acid

Wang,

Marks,

Fortenberry

et al. 2024

Sci. Adv.

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Glyceric acid [HOCH 2 CH(OH)COOH]—the simplest sugar acid—represents a key molecule in biochemical processes vital for metabolism in living organisms such as glycolysis. Although critically linked to the origins of life and identified in carbonaceous meteorites with abundances comparable to amino acids, the underlying mechanisms of its formation have remained elusive. Here, we report the very first abiotic synthesis of racemic glyceric acid via the barrierless radical-radical reaction of the hydroxycarbonyl radical (HOĊO) with 1,2-dihydroxyethyl (HOĊHCH 2 OH) radical in low-temperature carbon dioxide (CO 2 ) and ethylene glycol (HOCH 2 CH 2 OH) ices. Using isomer-selective vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry, glyceric acid was identified in the gas phase based on the adiabatic ionization energies and isotopic substitution studies. This work reveals the key reaction pathways for glyceric acid synthesis through nonequilibrium reactions from ubiquitous precursor molecules, advancing our fundamental knowledge of the formation pathways of key biorelevant organics—sugar acids—in deep space.

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Mechanical Interatomic Bond Formation in Ethanol and Methanol–Ethanol Mixture by Laser‐Driven Shock Waves

Ishikawa,

Sato

2024

ChemPhysChem

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Molecules, which were predicted to be produced by C–C or C–O bond formation between ethanol molecules induced by a laser‐driven shock wave, were identified by gas chromatography–mass spectrometry. Moreover, the laser irradiation of a methanol–ethanol mixture revealed the formation of C–C and C–O bonds between both components. Particularly, four hemiacetals (methoxymethanol, 1‐methoxyethanol, ethoxymethanol, and 1‐ethoxyethanol) were identified in the Ar‐saturated alcohol samples, whereas acetalization dominated sufficiently in the CO2‐saturated samples, significantly reducing the hemiacetals. It was verified that some molecules were produced by the dropout of an ethanol part during the C–C or C–O bond formation, supporting the contribution of laser‐driven shock waves.

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Quantum Tunneling Mediated Low-Temperature Synthesis of Interstellar Hemiacetals

Cited by 7 publications

References 41 publications

Methanetriol─Formation of an Impossible Molecule

Methanetriol─Formation of an Impossible Molecule

Interstellar formation of glyceric acid [HOCH ₂ CH(OH)COOH]—The simplest sugar acid

Mechanical Interatomic Bond Formation in Ethanol and Methanol–Ethanol Mixture by Laser‐Driven Shock Waves

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Quantum Tunneling Mediated Low-Temperature Synthesis of Interstellar Hemiacetals

Cited by 7 publications

References 41 publications

Methanetriol─Formation of an Impossible Molecule

Methanetriol─Formation of an Impossible Molecule

Interstellar formation of glyceric acid [HOCH 2 CH(OH)COOH]—The simplest sugar acid

Mechanical Interatomic Bond Formation in Ethanol and Methanol–Ethanol Mixture by Laser‐Driven Shock Waves

Contact Info

Product

Resources

About

Interstellar formation of glyceric acid [HOCH ₂ CH(OH)COOH]—The simplest sugar acid