Selected ion flow tube cation–molecule reaction studies and threshold photoelectron photoion coincidence spectroscopy of cyclic-C5F8

Parkes, Michael A.; Ali, Sahangir; Tuckett, Richard P.; Mikhailov, Victor A.; Mayhew, Chris A.

doi:10.1039/b704862a

Cited by 4 publications

(9 citation statements)

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“…This arises because autoionization from high-lying Rydberg states, which are parts of series converging to higher ionization thresholds, contribute to the intensity in the higher ionization energy region of the TPE spectrum. This effect has been observed before in two other fluorinated hydrocarbons, CF 3 CHF 2 and c -C 5 F 8 …”

Section: Discussionsupporting

confidence: 80%

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Study of 2-H-Heptafluoropropane and Its Thermal Decomposition Using UV Photoelectron Spectroscopy and ab Initio Molecular Orbital Calculations

et al. 2010

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The thermal decomposition of 2-H-heptafluoropropane, CF(3)CHFCF(3), at low pressure, heavily diluted in argon, has been studied over the temperature range 600-2000 degrees C using photoelectron spectroscopy. Comparison of the results obtained has been made with results of recent electronic structure calculations of possible decomposition pathways and results of a shock tube study. The most favored reaction thermodynamically, to produce CF(3)CF=CF(2) + HF, is found to be the main decomposition reaction at lower temperatures, 600-900 degrees C. At higher temperatures, 900-1200 degrees C, the decomposition reaction to give C(2)F(4) + CF(3)H was found to become important. No evidence for CF(3)CHFCF(3) --> CF(3)CHF + CF(3), a reaction expected to be important from a shock tube study, performed at much higher pressures, or for CF(3)CHFCF(3) --> CF(3)CF + CF(3)H was obtained, although for the latter reaction it is likely that CF(3)CF converts into C(2)F(4) under the conditions used before photoionization, in the ionization region of the photoelectron spectrometer. At higher temperatures C(3)F(6) decomposes to C(2)F(4) + CF(2), and C(2)F(4) decomposes to CF(2). Ab initio calculations have been performed of the adiabatic and vertical ionization energies of possible primary pyrolysis products to assist assignment of the photoelectron spectra recorded for heated flowing gas samples. A comparison is made between the threshold photoelectron spectrum and the photoelectron spectrum of CF(3)CF=CF(2).

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Section: Discussionsupporting

confidence: 80%

“…This effect has been observed before in two other fluorinated hydrocarbons, CF 3 CHF 2 1 and c-C 5 F 8 . 54…”

Section: Discussionmentioning

confidence: 99%

Study of 2-H-Heptafluoropropane and Its Thermal Decomposition Using UV Photoelectron Spectroscopy and ab Initio Molecular Orbital Calculations

et al. 2010

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“…Indeed, a review of the literature reveals little experimental data for c-C 5 F 8 , these being limited to some measurements of the electron attachment line shapes and cross sections at ultralow electron energies . Recent studies on the ionization cross sections of Jiao et al on cation−molecule reactions and Parkes et al on threshold photoelectron−photoion coincidence spectroscopy with a He(I) PES obtained with a lower resolution that in the present work have been reported. Quantum chemical studies via configuration interaction scheme (CIS) with the Hartree−Fock method 8 and ab initio calculations on the dissociative attachment resonance energies with comparisons to electron attachment mass spectrometric measurements 9 have also been discussed in a recent work, but the former has proven to disagree with our present calculations (see Computational Method section).…”

Section: Introductionmentioning

confidence: 57%

Electronic State Spectroscopy of c-C₅F₈ Explored by Photoabsorption, Electron Impact, Photoelectron Spectroscopies and Ab Initio Calculations

et al. 2008

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The electronic transitions and resonance-enhanced vibrational excitations of octafluorocyclopentene (c-C5F8) have been investigated using high-resolution photoabsorption spectroscopy in the energy range 6-11 eV. In addition, the high-resolution electron energy loss spectrum (HREELS) was recorded under the electric dipolar excitation conditions (100 eV incident energy, approximately 0 degrees scattering angle) over the 5-14 eV energy loss range. A He(I) photoelectron spectrum (PES) has also been recorded between 11 and 20 eV, allowing us to derive a more precise value of (11.288 +/- 0.002) eV for the ground neutral state adiabatic ionization energy. All spectra presented in this paper represent the first and highest resolution data yet reported for octafluorocyclopentene. Ab initio calculations have been performed for helping in the assignment of the spectral bands for both neutral excited states and ionic states.

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“…including our recent studies on the isomers of dichloroethene. 3,13,31 The reactions of Xe + and Ar + with monochloroethene have previously been studied in a two-stage ion-beam mass spectrometer by Izod and Tedder. 10 Figure 1 (b)-(e) the branching ratios from the photon-induced TPEPICO data using continuously-tunable vacuum-UV radiation for the three dichloroethenes and trichloroethene are also plotted as continuous lines.…”

Section: Ion-molecule Branching Ratiosmentioning

confidence: 99%

Selected Ion Flow Tube Study of the Ion−Molecule Reactions of Monochloroethene, Trichloroethene, and Tetrachloroethene

et al. 2008

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Data for the rate coefficients and product cations of the reactions of a large number of atomic and small molecular cations with monochloroethene, trichloroethene, and tetrachloroethene in a selected ion flow tube at 298 K are reported. The recombination energy of the ions range from 6.27 (H3O(+)) through to 21.56 (Ne(+)) eV. Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental values. Thermochemistry and mass balance predict the most feasible neutral products. Together with previously reported results for the three isomers of dichloroethene ( Mikhailov, V. A. ; Parkes, M. A. ; Tuckett, R. P. ; Mayhew, C. A. J. Phys. Chem. A 2006, 110, 5760 ), the fragment ion branching ratios have been compared with those from threshold photoelectron photoion coincidence spectroscopy over the photon energy range of 9-22 eV to determine the importance or otherwise of long-range charge transfer. For ions with recombination energy in excess of the ionization energy of the chloroethene, charge transfer is energetically allowed. The similarity of the branching ratios from the two experiments suggest that long-range charge transfer is dominant. For ions with recombination energy less than the ionization energy, charge transfer is not allowed; chemical reaction can only occur following formation of an ion-molecule complex, where steric effects are more significant. The products that are now formed and their percentage yields are a complex interplay between the number and position of the chlorine atoms with respect to the C=C bond, where inductive and conjugation effects can be important.

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Selected ion flow tube cation–molecule reaction studies and threshold photoelectron photoion coincidence spectroscopy of cyclic-C5F8

Cited by 4 publications

References 40 publications

Study of 2-H-Heptafluoropropane and Its Thermal Decomposition Using UV Photoelectron Spectroscopy and ab Initio Molecular Orbital Calculations

Study of 2-H-Heptafluoropropane and Its Thermal Decomposition Using UV Photoelectron Spectroscopy and ab Initio Molecular Orbital Calculations

Electronic State Spectroscopy of c-C₅F₈ Explored by Photoabsorption, Electron Impact, Photoelectron Spectroscopies and Ab Initio Calculations

Selected Ion Flow Tube Study of the Ion−Molecule Reactions of Monochloroethene, Trichloroethene, and Tetrachloroethene

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Selected ion flow tube cation–molecule reaction studies and threshold photoelectron photoion coincidence spectroscopy of cyclic-C5F8

Cited by 4 publications

References 40 publications

Study of 2-H-Heptafluoropropane and Its Thermal Decomposition Using UV Photoelectron Spectroscopy and ab Initio Molecular Orbital Calculations

Study of 2-H-Heptafluoropropane and Its Thermal Decomposition Using UV Photoelectron Spectroscopy and ab Initio Molecular Orbital Calculations

Electronic State Spectroscopy of c-C5F8 Explored by Photoabsorption, Electron Impact, Photoelectron Spectroscopies and Ab Initio Calculations

Selected Ion Flow Tube Study of the Ion−Molecule Reactions of Monochloroethene, Trichloroethene, and Tetrachloroethene

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Electronic State Spectroscopy of c-C₅F₈ Explored by Photoabsorption, Electron Impact, Photoelectron Spectroscopies and Ab Initio Calculations