Direct evidence for a radiation-induced synthesis of acetonitrile and isoacetonitrile from a 1 : 1 CH<sub>4</sub>⋯HCN complex at cryogenic temperatures: is it a missing link between inorganic and prebiotic astrochemistry?

Volosatova, Anastasia D.; Lukianova, Mariia A.; Zasimov, Pavel V.; Feldman, Vladimir I.

doi:10.1039/d1cp01598b

Cited by 11 publications

(7 citation statements)

References 83 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Nevertheless, detailed information on its spectroscopic properties and dynamics in different media was limited for a long time. It is worth noting that the CN • fundamental frequency is rather specific and characteristic (the absorption band at 2240-2244 cm −1 was observed in various matrices [116][117][118]). However, it is a poor IR absorber, which may preclude its detection if it occurs in low concentration.…”

Section: The Radicals Related To Hcnmentioning

confidence: 99%

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

Feldman

2023

IJMS

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: The Radicals Related To Hcnmentioning

confidence: 99%

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

Feldman

2023

IJMS

Self Cite

View full text Add to dashboard Cite

show abstract

“…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

View full text Add to dashboard Cite

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.

show abstract

“…It is worth noting that, in most cases, the relatively weak CO complexes with various molecules can be easily obtained and stabilized in matrices in sufficiently high amounts through a common codeposition procedure, which makes them very convenient objects for model studies using matrix isolation. Recently, we demonstrated the potentiality of matrix isolation for the investigation of the mechanisms of synthetic radiation-induced processes occurring in some astrochemically relevant intermolecular complexes. − It is to be mentioned that such strategy was also applied to radiation chemistry of the HCN···CO complex; however, no clear evidence for the formation of synthetic N-, C-, and O-containing products was found in this case . Here, we are focusing on the radiation-induced chemistry of an isolated NH 3 ···CO complex as one of the most plausible precursors of formamide and some other functional COMs in ISM.…”

Section: Introductionmentioning

confidence: 99%

The Radiation Chemistry of NH₃···CO Complex in Cryogenic Media as Studied by Matrix Isolation

2022

Self Cite

View full text Add to dashboard Cite

The NH3···CO complex can be considered an important building block for cold synthetic astrochemistry leading to the formation of complex organic molecules, including key prebiotic species. In this work, we have studied the radiation-induced transformations of this complex in Ar, Kr, and Xe matrices using FTIR spectroscopy. On the basis of comparison with the quantum chemical calculations at the CCSD(T)/L2a_3 level of theory, it was found that the initial complex had the configuration with hydrogen bonding through the carbon atom of CO. Irradiation of the matrix isolated complex with X-rays at 6 K leads to the formation of a number of synthetic products, namely, HNCO (in all matrices), formamide NH2CHO, NH2CO, and HNCO-H2 (in argon and krypton). The matrix effect on the product distribution was explained by the involvement of different excited states of the complex in their formation. It was suggested that formamide results from the singlet excited states while other species mainly originate from triplet excited states. The latter states are efficiently populated through ion-electron recombination (in all matrices) and through intersystem crossing (particularly, in xenon). High yield of the recombination triplet states is a feature of the processes induced by high-energy radiation (in contrast to direct photolysis). NCO, CN, and NO were found as minor secondary products at high adsorbed doses. The astrochemical implications of the obtained results are discussed.

show abstract

Direct evidence for a radiation-induced synthesis of acetonitrile and isoacetonitrile from a 1 : 1 CH₄⋯HCN complex at cryogenic temperatures: is it a missing link between inorganic and prebiotic astrochemistry?

Abstract: Nitriles are important constituents of the extraterrestrial media. Nitriles are supposed to play a crucial role in the prebiotic chemistry occurring in the interstellar medium. In this work, we have...

Cited by 11 publications

References 83 publications

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

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

The Radiation Chemistry of NH₃···CO Complex in Cryogenic Media as Studied by Matrix Isolation

Contact Info

Product

Resources

About

Direct evidence for a radiation-induced synthesis of acetonitrile and isoacetonitrile from a 1 : 1 CH4⋯HCN complex at cryogenic temperatures: is it a missing link between inorganic and prebiotic astrochemistry?

Abstract: Nitriles are important constituents of the extraterrestrial media. Nitriles are supposed to play a crucial role in the prebiotic chemistry occurring in the interstellar medium. In this work, we have...

Cited by 11 publications

References 83 publications

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

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

The Radiation Chemistry of NH3···CO Complex in Cryogenic Media as Studied by Matrix Isolation

Contact Info

Product

Resources

About

Direct evidence for a radiation-induced synthesis of acetonitrile and isoacetonitrile from a 1 : 1 CH₄⋯HCN complex at cryogenic temperatures: is it a missing link between inorganic and prebiotic astrochemistry?

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

The Radiation Chemistry of NH₃···CO Complex in Cryogenic Media as Studied by Matrix Isolation