New prebiotic molecules in the interstellar medium from the reaction between vinyl alcohol and CN radicals: unsupervised reaction mechanism discovery, accurate electronic structure calculations and kinetic simulations

Ballotta, Bernardo; Martínez-Núñez, Emilio; Rampino, Sergio; Barone, Vincenzo

doi:10.1039/d3cp02571c

Cited by 3 publications

(1 citation statement)

References 65 publications

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“…Since the first identification of vinyl alcohol (CH 2 CHOH) in the interstellar medium (ISM) by Turner et al (Turner & Apponi 2001) two decades ago toward the dense molecular cloud Sagittarius B2(N), enols-alkenes carrying a hydroxyl group at a carbon-carbon double bond-have received considerable attention from the astrochemistry (Abplanalp et al 2016b;, synthetic organic chemistry (Mardyukov et al 2021(Mardyukov et al , 2023, physical chemistry (Taatjes et al 2005;Rösch et al 2021;Melosso et al 2022), and theoretical chemistry (Elango et al 2010;Ballotta et al 2023;Mó et al 2023;Würmel & Simmie 2024) communities. This interest is mainly due to their key role as reactive intermediates in the synthesis of biorelevant molecules related to the Origins of Life.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Acetylenediol (HOCCOH) and Glyoxal (HCOCHO) in Interstellar Analog Ices of Carbon Monoxide and Water

Wang,

Turner,

Marks

et al. 2024

ApJ

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Enols—tautomers of ketones or aldehydes—are considered key intermediates in the formation of prebiotic sugars and sugar acids. Although laboratory simulation experiments suggest that enols should be ubiquitous in the interstellar medium, the underlying formation mechanisms of enols in interstellar environments are largely elusive. Here, we present the laboratory experiments on the formation of glyoxal (HCOCHO) along with its ynol tautomer acetylenediol (HOCCOH) in interstellar ice analogs composed of carbon monoxide (CO) and water (H2O) upon exposure to energetic electrons as a proxy for secondary electrons generated from Galactic cosmic rays. Utilizing tunable vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry, glyoxal and acetylenediol were detected in the gas phase during temperature-programmed desorption. Our results reveal the formation pathways of glyoxal via radical–radical recombination of two formyl (HĊO) radicals, and that of acetylenediol via keto-enol-ynol tautomerization. Due to the abundance of carbon monoxide and water in interstellar ices, glyoxal and acetylenediol are suitable candidates for future astronomical searches. Furthermore, the detection of acetylenediol in astrophysically relevant ices advances our understanding for the formation pathways of high-energy tautomers such as enols in deep space.

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Section: Introductionmentioning

confidence: 99%

Preparation of Acetylenediol (HOCCOH) and Glyoxal (HCOCHO) in Interstellar Analog Ices of Carbon Monoxide and Water

Wang,

Turner,

Marks

et al. 2024

ApJ

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Reduced Cost Computation and Exploitation of Accurate Radial Interaction Potentials for Barrier-Less Processes

Crisci,

Ballotta,

Mendolicchio

et al. 2024

J. Chem. Theory Comput.

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Barrier-less steps are typical of radical and ionic reactions in the gas-phase, which often take place in extreme environments such as the combustion reactors operating at very high temperatures or the interstellar medium, characterized by ultralow temperatures and pressures. The difficulty of experimental studies in conditions mimicking these environments suggests that computational approaches can provide a valuable support. In this connection, the most advanced treatments of these processes in the framework of transition state theory are able to deliver accurate kinetic parameters provided that the underlying potential energy surface is sufficiently accurate. Since this requires a balanced treatment of static and dynamic correlation (which play different roles in different regions), very sophisticated and expensive quantum chemical approaches are required. One effective solution of this problem is offered by the computation of accurate one-dimensional radial potentials, which are then used to correct the results of a Monte Carlo sampling performed by cheaper quantum chemical approaches. In this paper, we will show that, for a large panel of different barrier-less reaction steps, the radial potential is ruled by the R −4 term and that addition of a further R −6 contribution provides quantitative agreement with the reference points. The consequences of this outcome are not trivial, since the reference potential can be fitted by a very limited number of points possibly with a nonlinear spacing. In the case of reaction steps ruled by long-range transition states, generalized expressions are also given for computing reaction rates in the framework of the phase-space theory. All these improvements pave the way toward the computation of reaction rates for barrier-less reactions involving large molecules.

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Unfruitful chemical pathway for interstellar furan: formation of the four isomers of 1-butenol-3-yne

García de la Concepción,

Rivilla

2024

Monthly Notices of the Royal Astronomical Society

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Heterocycles have not been detected in the interstellar medium (ISM) yet. However, the direct involvement of some pentagonal heterocycles within the formation of key biomolecules for the origin of life makes the search for these systems in the ISM relevant for understanding whether some of the bricks of life could be formed in the ISM. We have explored the possible formation of the simple heterocycle furan (c-C4H4O) under interstellar conditions, through the reaction between two interstellar species, syn-vinyl alcohol (syn-VA) and the CCH radical. We employed state-of-the-art quantum-chemical calculations to elucidate the reaction mechanism between the reaction of CCH radical and syn-VA. Kinetic simulations were carried out aiming to quantitatively assess the viability of this reaction in the ISM. We have found a reaction pathway to furan where all energy barriers are submerged. However, the formation of this heterocycle is not feasible because the intermediates leading to furan can evolve through more favourable routes. In contrast, we have found viable pathways for the formation of the four isomers of 1-butenol-3-yne (HCCCHCHOH) (Z-syn, E-syn, E-anti and Z-anti), which thus are promising species to be detected in the ISM. Our theoretical work indicates that the four isomers of 1-butenol-3-yne should be present in the ISM, because the precursors are known interstellar species, and the kinetic simulations indicates that their formation is very likely. We then encourage the observational search of these molecules in the ISM.

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New prebiotic molecules in the interstellar medium from the reaction between vinyl alcohol and CN radicals: unsupervised reaction mechanism discovery, accurate electronic structure calculations and kinetic simulations

Abstract: Vinyl alcohol (VyA) and cyanide radical (CN) are relatively abundant in the interstellar medium (ISM). VyA is the enolic tautomer of acetaldehyde and has two low-lying conformers, characterized by the...

Cited by 3 publications

References 65 publications

Preparation of Acetylenediol (HOCCOH) and Glyoxal (HCOCHO) in Interstellar Analog Ices of Carbon Monoxide and Water

Preparation of Acetylenediol (HOCCOH) and Glyoxal (HCOCHO) in Interstellar Analog Ices of Carbon Monoxide and Water

Reduced Cost Computation and Exploitation of Accurate Radial Interaction Potentials for Barrier-Less Processes

Unfruitful chemical pathway for interstellar furan: formation of the four isomers of 1-butenol-3-yne

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