1,1,1,2-tetrafluoroethane photofragmentation: a translational kinetic energy release analysis in the EUV and X-ray energies range

Bonfim, Victor S.; Prazeres, Ítalo; Morcelle, V.; Marinho, Ricardo R. T.; Arruda, Manuela S.; Mendes, Luiz A. Vieira; Ribeiro, Leonardo C.; Santos, Mabele J.; Medina, Aline; Santos, A. C. F.

doi:10.1080/00268976.2022.2100836

Cited by 1 publication

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“…, the CHF 2 + formation process within each investigated channel involves several distinct elementary steps. In accordance with the figure, each of the proposed elementary reactions shown is further detailed below, accompanied by the corresponding ΔH 298 values [DLPNO-CCSD(T)/CBS//M06-2X/cc-pVTZ]:HF rearrangement pathway, CF 3 CH 2 F → CF 3 CH 2 F + + e − ΔH 298 = 12.30 eV,(11) …”

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confidence: 76%

“…Introduced to replace R-12 (dichlorodifluoromethane, CCl 2 F 2 ), it has become the most abundant hydrofluorocarbon (HFC) in the atmosphere, as reported by Harrison et al 1 Since the beginning of its commercial usage, CF 3 CH 2 F has been the subject of numerous experimental studies concerning the effects of ionizing radiation. [2][3][4][5][6][7][8][9][10][11] With a few exceptions, 10,11 most of them focused on valence ionization (more details on other CF 3 CH 2 F irradiation experiments are given elsewhere 11 ). In the realm of computational studies centered on R-134a, a substantial body of research has also emerged, [12][13][14][15][16][17] the most recent of which is by our group.…”

Section: Introductionmentioning

confidence: 99%

“…Calculations are at the DLPNO-CCSD(T)/CBS//M06-2X/cc-pVTZ level of theory. Mean deviation: −0.29 ± 0.07 eV, considering only reactions (3), (4), and(11).…”

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confidence: 99%

“…The negative signs indicate that the ΔH 298 values are smaller than the corresponding AEs. When we consider these deviations along with reaction(11), the average deviation amounts to −0.29 ± 0.07 eV.TableIalso presents the AE of CHF 2 + (16.11 eV) and compares it with the formation of CHF 2…”

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confidence: 99%

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Deciphering the irradiation induced fragmentation–rearrangement mechanisms in valence ionized CF3CH2F

Bonfim,

Souza,

de Oliveira

et al. 2024

The Journal of Chemical Physics

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The increasing presence of 1,1,1,2-tetrafluoroethane (CF3CH2F) in the atmosphere has prompted detailed studies into its complex photodissociation behavior. Experiments focusing on CF3CH2F irradiation have unveiled an array of ions, with the persistent observation of the rearrangement product CHF2+ not yet fully understood. In this work, we combine density functional theory, coupled-cluster calculations with a complete basis set formalism, and atom-centered density matrix propagation molecular dynamics to investigate the energetics and dynamics of different potential pathways leading to CHF2+. We found that the two-body dissociation pathway involving an HF rearrangement, which was previously considered complex for CHF2+ formation, is actually straightforward but not likely due to the facile loss of HF. In contrast, our calculations reveal that the H elimination pathway, once thought of as a potential route to CHF2+, is not only comparably disadvantageous from both thermodynamic and kinetic points of view but also does not align with experimental data, particularly the lack of a rebound peak at m/z 101–102. We establish that the formation of CHF2+ is predominantly via the HF elimination channel, a conclusion experimentally corroborated by studies involving the trifluoroethylene cation CF2CHF+, a key intermediate in this process.

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confidence: 76%

Section: Introductionmentioning

confidence: 99%

“…Calculations are at the DLPNO-CCSD(T)/CBS//M06-2X/cc-pVTZ level of theory. Mean deviation: −0.29 ± 0.07 eV, considering only reactions (3), (4), and(11).…”

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confidence: 99%

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confidence: 99%

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