Radiation-induced transformations of HCN⋯C2H2, HCN⋯C2H4 and HCN⋯C2H6 complexes in noble gas matrices: Synthesis of C3HxN molecules in cryogenic media

Lukianova, Mariia A.; Volosatova, Anastasia D.; Drabkin, Vladimir D.; Sosulin, Ilya S.; Kameneva, Svetlana V.; Feldman, Vladimir I.

doi:10.1016/j.radphyschem.2020.109232

Cited by 11 publications

(3 citation statements)

References 40 publications

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“…It should be noted that, unlike the reactions of neutral radical–molecule complexes (see, for example, refs – ), the structure and chemical dynamics of charged open-shell species produced by ionization of complexes in matrices is poorly studied from both experimental and theoretical points of view. We may note that the studies of the radiation-induced evolution of complexes are particularly useful for modeling cold astrochemical processes occurring within the “building blocks” (recent examples may be found in refs and – ). Most probably, this evolution taking place both in matrices and in mixed ices − includes the formation of complex radical cations as intermediates; however, direct pieces of evidence on this hidden stage are quite limited due to the rapid recombination of primary cations with electrons or their secondary reactions.…”

Section: Introductionmentioning

confidence: 99%

Formation and Evolution of H₂C₃O^+•Radical Cations: A Computational and Matrix Isolation Study

et al. 2022

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The family of isomeric H2C3O+• radical cations is of great interest for physical organic chemistry and chemistry occurring in extraterrestrial media. In this work, we have experimentally examined a unique synthetic route to the generation of H2C3O+• from the C2H2···CO intermolecular complex and also considered the relative stability and monomolecular transformations of the H2C3O+• isomers through high-level ab initio calculations. The structures, energetics, harmonic frequencies, hyperfine coupling constants, and isomerization pathways for several of the most important H2C3O+• isomers were calculated at the UCCSD(T) level of theory. The complementary FTIR and EPR studies in argon matrices at 5 K have demonstrated that the ionized C2H2···CO complex transforms into the E-HCCHCO+• isomer, and this latter species is supposed to be the key intermediate in further chemical transformations, providing a remarkable piece of evidence for kinetic control in low-temperature chemistry. Photolysis of this species at λ = 410–465 nm results in its transformation to the thermodynamically most stable H2CCCO+• isomer. Possible implications of the results and potentiality of the proposed synthetic strategy to the preparation of highly reactive organic radical cations are discussed.

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Section: Introductionmentioning

confidence: 99%

Formation and Evolution of H₂C₃O^+•Radical Cations: A Computational and Matrix Isolation Study

et al. 2022

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“…In this situation, the pre-existing building blocks consisting of two or more molecules should play a crucial role. In order to understand the basic mechanisms involved in the processes of cold synthetic transformations, we have introduced a general concept based on model studies of the radiation chemistry of 1:1 intermolecular complexes isolated in rigid inert media [94,95,112,117,125,134,[136][137][138][139][140][141]. It should be emphasized that the interaction in such complexes is typically rather weak (the computed interaction energy usually does not exceed 2-4 kcal/mol); however, it is more than sufficient to fix the pre-determined geometry in solid cryogenic matrices, and thus, to control further radiation-induced transformations.…”

Section: Identification Of Radical-molecule Complexes and Their Possi...mentioning

confidence: 99%

Astrochemically Relevant Radicals and Radical–Molecule Complexes: A New Insight from Matrix Isolation

Feldman

2023

IJMS

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The reactive open-shell species play a very important role in the radiation-induced molecular evolution occurring in the cold areas of space and presumably leading to the formation of biologically relevant molecules. This review presents an insight into the mechanism of such processes coming from matrix isolation studies with a main focus on the experimental and theoretical studies performed in the author’s laboratory during the past decade. The radicals and radical cations produced from astrochemically relevant molecules were characterized by Fourier transform infrared (FTIR) and electron paramagnetic resonance (EPR) spectroscopy. Small organic radicals containing C, O, and N atoms are considered in view of their possible role in the formation of complex organic molecules (COMs) in space, and a comparison with earlier results is given. In addition, the radical–molecule complexes generated from isolated intermolecular complexes in matrices are discussed in connection with their model significance as the building blocks for COMs formed under the conditions of extremely restricted molecular mobility at cryogenic temperatures.

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“…One of the most abundant molecules detected in space is hydrogen cyanide (HCN). − Numerous studies show noncovalent bonding interactions between HCN and other molecules. These interactions range from hydrogen-bonding to halogen-bonding interactions, where HCN can donate or accept electron density. − Complexation of HCN with other molecules can also affect the transformation of HCN, in some cases catalyzing the isomerization from HCN to HNC, which has important consequences to our understanding of the sources and sinks of these two isomers. − Studying the reactivity of HCN and its oligomers in astrophysical objects is of interest as HCN is an important building block for amino acids and other life-bearing polymers. − In order to advance studies of amino acid and life-bearing polymer formation in space, a complete chemical understanding of their precursors, such as HCN, under interstellar conditions is necessary.…”

Section: Introductionmentioning

confidence: 99%

Weakly Bound Complex Formation between HCN and CH₃Cl: A Matrix-Isolation and Computational Study

et al. 2022

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The matrix-isolated infrared spectrum of a hydrogen cyanide–methyl chloride complex was investigated in a solid argon matrix. HCN and CH3Cl were co-condensed onto a substrate held at 10 K with an excess of argon gas, and the infrared spectrum was measured using Fourier-transform infrared spectroscopy. Quantum chemical geometry optimization, harmonic frequency, and natural bonding orbital calculations indicate stabilized hydrogen- and halogen-bonded structures. The two resulting weakly bound complexes are both composed of one CH3Cl molecule bound to a (HCN)3 subunit, where the three HCN molecules are bound head-to-tail in a ring formation. Our study suggests thatin the presence of CH3Clthe formation of (HCN)3 is promoted through complexation. Since HCN aggregates are an important precursor to prebiotic monomers (amino acids and nucleobases) and other life-bearing polymers, this study has astrophysical implications toward the search for life in space.

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Radiation-induced transformations of HCN⋯C2H2, HCN⋯C2H4 and HCN⋯C2H6 complexes in noble gas matrices: Synthesis of C3HxN molecules in cryogenic media

Cited by 11 publications

References 40 publications

Formation and Evolution of H₂C₃O^+•Radical Cations: A Computational and Matrix Isolation Study

Formation and Evolution of H₂C₃O^+•Radical Cations: A Computational and Matrix Isolation Study

Astrochemically Relevant Radicals and Radical–Molecule Complexes: A New Insight from Matrix Isolation

Weakly Bound Complex Formation between HCN and CH₃Cl: A Matrix-Isolation and Computational Study

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Radiation-induced transformations of HCN⋯C2H2, HCN⋯C2H4 and HCN⋯C2H6 complexes in noble gas matrices: Synthesis of C3HxN molecules in cryogenic media

Cited by 11 publications

References 40 publications

Formation and Evolution of H2C3O+•Radical Cations: A Computational and Matrix Isolation Study

Formation and Evolution of H2C3O+•Radical Cations: A Computational and Matrix Isolation Study

Astrochemically Relevant Radicals and Radical–Molecule Complexes: A New Insight from Matrix Isolation

Weakly Bound Complex Formation between HCN and CH3Cl: A Matrix-Isolation and Computational Study

Contact Info

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Formation and Evolution of H₂C₃O^+•Radical Cations: A Computational and Matrix Isolation Study

Formation and Evolution of H₂C₃O^+•Radical Cations: A Computational and Matrix Isolation Study

Weakly Bound Complex Formation between HCN and CH₃Cl: A Matrix-Isolation and Computational Study