On the formation of 2- and 3-cyanofurans and their protonated forms in interstellar medium conditions: quantum chemical evidence

Simbizi, René; Nduwimana, Désiré; Niyoncuti, Joël; Cishahayo, Prosper; Gahungu, Godefroid

doi:10.1039/d2ra04351c

Cited by 5 publications

(11 citation statements)

References 69 publications

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“…Thus, the PA 2-furonitrile must be above that of water (accepted literature value of PA(H 2 O) = 691 kJ mol −1 [13]). This observation agrees with a very recent theoretical publication that provides for site 5 a PA of 747 kJ mol −1 at 298 K [18]. This has been independently confirmed by us, also at 298 K, using the density function theory calculation that used the Gaussian09W program with the GaussView05 for Windows interface and the B3LYP functional with 6-31 + G(d,p) basis set [19].…”

Section: Acrylonitrilesupporting

confidence: 91%

Revealing the Ion Chemistry Occurring in High Kinetic Energy-Ion Mobility Spectrometry: A Proof of Principle Study

et al. 2023

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Here, we present proof of principle studies to demonstrate how the product ions associated with the ion mobility peaks obtained from a High Kinetic Energy-Ion Mobility Spectrometer (HiKE-IMS) measurement of a volatile can be identified using a Proton Transfer Reaction/Selective Reagent Ion-Time-of-Flight-Mass Spectrometer (PTR/SRI-ToF-MS) when operating both instruments at the same reduced electric field value and similar humidities. This identification of product ions improves our understanding of the ion chemistry occurring in the ion source region of a HiKE-IMS. The combination of the two analytical techniques is needed, because in the HiKE-IMS three reagent ions (NO+, H3O+ and O2+•) are present at the same time in high concentrations in the reaction region of the instrument for reduced electric fields of 100 Td and above. This means that even with a mass spectrometer coupled to the HiKE-IMS, the assignment of the product ions to a given reagent ion to a high level of confidence can be challenging. In this paper, we demonstrate an alternative approach using PTR/SRI-ToF-MS that allows separate investigations of the reactions of the reagent ions NO+, H3O+ and O2+•. In this study, we apply this approach to four nitrile containing organic compounds, namely acetonitrile, 2-furonitrile, benzonitrile and acrylonitrile. Both the HiKE-IMS and the PTR/SRI-ToF-MS instruments were operated at a commonly used reduced electric field strength of 120 Td and with gas flows at the same humidities.

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Section: Acrylonitrilesupporting

confidence: 91%

Revealing the Ion Chemistry Occurring in High Kinetic Energy-Ion Mobility Spectrometry: A Proof of Principle Study

et al. 2023

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“…The protonation of furan was studied in an earlier work with the aid of G2MP2 and G3. 26 The results presented in Table 2 show the a-carbon (C a ) to be the preferential site of protonation of furan (in line with the literature), but also that G4 is the most accurate method to calculate the PA. In comparison with all computed values, a PA of 813.62 kJ mol À1 at 298.15 K (based on G4) is closer to the NIST value (812 kJ mol À1 ) for furan.…”

Section: Protonation Of Dicyanofuranssupporting

confidence: 83%

“…33 The geometrical structures were found following the methodologies used earlier. 30,32 The B3LYP 33,34 /6-31G(d,p) 35 level of theory for neutral and protonated forms was used for geometrical optimization, followed by empirical corrections. This level of theory was chosen based on its successful use in other works.…”

Section: Computational Detailsmentioning

confidence: 99%

“…23,24 Lattelais and coworkers (2010) reported that pyrrole (C 4 H 5 N), furan (C 4 H 4 O) and thiophene (C 4 H 4 S) isomers are stable at ISM temperatures of 10-50 K. 25 Quantum chemical evidence of the spontaneous protonation of 2-furonitrile and 3-furonitrile (also called furan-2/3-carbonitrile) under ISM conditions were recently provided. 26 However, the spectroscopic and thermodynamic data required to detect new protonated aromatic species are lacking.…”

Section: Introductionmentioning

confidence: 99%

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Spontaneous formation and protonation of dicyanofuran isomers under physical conditions found in interstellar space: quantum chemical insights into thermodynamics and spectroscopy

Simbizi,

Abdalla,

Bukuru

et al. 2024

New J. Chem.

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“…Each of these species has a substantial increase in its dipole moment relative to furan, as a consequence of cyano substitution. Additionally, Simbizi et al recently determined that the formation of furan, 2-furonitrile, and 3-furonitrile is thermodynamically favored in the conditions of the ISM . For the first time, we present the rotational spectra and transition frequencies of 2-furonitrile.…”

Section: Introductionmentioning

confidence: 82%

Millimeter-Wave and High-Resolution Infrared Spectroscopy of 2-Furonitrile─A Highly Polar Substituted Furan

et al. 2023

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The rotational spectrum of 2-furonitrile (2-cyanofuran) has been obtained from 140 to 750 GHz, capturing its most intense rotational transitions at ambient temperature. 2-Furonitrile is one of two isomeric cyano-substituted furan derivatives, both of which possess a substantial dipole moment due to the cyano group. The large dipole of 2-furonitrile allowed over 10 000 rotational transitions of its ground vibrational state to be observed and least-squares fit to partial octic, A-and S-reduced Hamiltonians with low statistical uncertainty (σ fit = 40 kHz). The high-resolution infrared spectrum, obtained at the Canadian Light Source, allowed for accurate and precise determination of the band origins of its three lowest-energy fundamental modes (ν 24 , ν 17 , and ν 23 ). Similar to other cyanoarenes, the first two fundamental modes (ν 24, A″, and ν 17 , A′, for 2-furonitrile) form an a-and b-axis Coriolis-coupled dyad. More than 7000 transitions from each of these fundamental states were fit to an octic A-reduced Hamiltonian (σ fit = 48 kHz), and the combined spectroscopic analysis determines fundamental energies of 160.1645522 (26) cm −1 and 171.9436561 (25) cm −1 for ν 24 and ν 17 , respectively. The least-squares fitting of this Coriolis-coupled dyad required 11 coupling terms,J , and F ac K . Using both the rotational and high-resolution infrared spectra, a preliminary least-squares fit was obtained for ν 23 , providing its band origin of 456.7912716 (57) cm −1 . The transition frequencies and spectroscopic constants provided in this work, when combined with theoretical or experimental nuclear quadrupole coupling constants, will provide the foundation for future radioastronomical searches for 2-furonitrile across the frequency range of currently available radiotelescopes.

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On the formation of 2- and 3-cyanofurans and their protonated forms in interstellar medium conditions: quantum chemical evidence

Abstract: The literature is still poor in theoretical and experimental, including both spectroscopic and thermodynamic, data for protonated furan and protonated 2-cyanofuran and 3-cyanofuran (FH+, 2CFH+ and 3CFH+).

Cited by 5 publications

References 69 publications

Revealing the Ion Chemistry Occurring in High Kinetic Energy-Ion Mobility Spectrometry: A Proof of Principle Study

Revealing the Ion Chemistry Occurring in High Kinetic Energy-Ion Mobility Spectrometry: A Proof of Principle Study

Spontaneous formation and protonation of dicyanofuran isomers under physical conditions found in interstellar space: quantum chemical insights into thermodynamics and spectroscopy

Millimeter-Wave and High-Resolution Infrared Spectroscopy of 2-Furonitrile─A Highly Polar Substituted Furan

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