Photoelectron spectroscopy of vinylbromide and intramolecular dynamics of the ionic B̃ state

Hoxha, A.; Locht, Robert; Leyh, Bernard; Dehareng, Dominique; Hottmann, K.; Baumgärtel, H.

doi:10.1016/s0301-0104(00)00052-5

Cited by 22 publications

(54 citation statements)

References 28 publications

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“…It has to be emphasized that the high-energy features observed between 10 eV and 20 eV in this PAS are by far stronger than in the PAS of C 2 H 3 Br [14]. Table 2 together with their quantum defects and convergence limits.…”

Section: Resultsmentioning

confidence: 76%

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The vacuum UV photoabsorption spectroscopy of vinyl fluoride (C2H3F): The vibrational fine structure and its analysis

et al. 2009

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The vacuum UV photoabsorption spectrum of C 2 H 3 F has been examined in detail between 6 eV and 25 eV photon energy by using synchrotron radiation. The analysis of the data is supported by ab initio quantum mechanical calculations applied to valence and Rydberg excited states of C 2 H 3 F. At 7.6 eV the π → π * and the 2a" → 3s transitions are observed. An analysis is proposed and applied to the mixed fine structure belonging to these transitions. For the π → π * transition one single long vibrational progression is observed with hcω e = 95 ± 7 meV (766 ± 56 cm -1 ) and its adiabatic excitation energy is 6.892 eV (55 588 cm -1 ). The 2a" → 3s transition is characterized by a single short progression with hcω e = 167 ± 10 meV (1350 ± 80 cm -1 ) starting at 6.974 eV (56 249 cm -1 ). From the present ab initio calculations these two wavenumbers best correspond to the vibrational modes υ 9 (CH 2 rock in-plane, FCC-bend) and υ 6 (CH 2 rock in-plane, CF stretch) calculated at 615 cm -1 in the π * state and 1315 cm -1 in the ( 2 A")3s Rydberg state respectively. The C=C stretching could not be excluded. The dense structured spectrum observed between 8.0 eV and 10.5 eV has been analyzed in terms of vibronic transitions to Rydberg states all converging to the C 2 H 3 F + (X A") ionic ground state. An analysis of the associated complex fine structure of the individual Rydberg states has been attempted providing average values of the wavenumbers, e.g., for the ( 2 A")3p Rydberg state hcω 9 = 60 ± 1 meV (or 484 ± 8 cm -1 ), hcω 7 = 151 ± 7 meV (or 1218 ± 60 cm -1 ), hcω 4 = 191 ± 3 meV (or 1540 ± 24 cm -1 ). The assignment of hcω = 105 ± 5 meV (or 823 ± 40 cm -1 ) is discussed. These experimental values are in good agreement with the theoretical predictions for C 2 H 3 F + [R. Locht, B. Leyh, D. Dehareng, K. Hottmann, H. Baumgärtel, Chem. Phys. (in press)]. Above 10.5 eV and up to 25 eV several broad and strong bands are tentatively assigned to transitions to valence (V-V) and/or Rydberg (V-R) states converging to excited ionic states of C 2 H 3 F.

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Section: Resultsmentioning

confidence: 76%

“…The systematic study of ethylene and of several of its halogen substituted derivatives has been initiated, e.g. for C 2 H 3 Cl [12,13], C 2 H 3 Br [14][15][16] and 1,1-C 2 H 2 F 2 [17,18], or is in progress using the same array of techniques. The vacuum UV spectroscopic data reported on vinyl fluoride are very scarce.…”

Section: Introductionmentioning

confidence: 99%

The vacuum UV photoabsorption spectroscopy of vinyl fluoride (C2H3F): The vibrational fine structure and its analysis

et al. 2009

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“…A linear regression fitted the data with a correlation coefficient of 0.989, including the errors on ∆G V . From the zero extrapolation and slope, the molecular constants (hcω 0 ) 4 After a drop of the relative intensities ( Fig. 2(a)), the structures observed above 10.850 eV have increasing intensities reaching a maximum at about 11.007 eV and then slowly decrease for photon energies increasing to 12.0 eV.…”

Section: The Experimental Datamentioning

confidence: 99%

“…The combination reported at 86 561 cm -1 for v 3 +4v 5 [23] has been allocated preferentially to the structure at 10.684 eV (Table 5), i.e. v 6 + 4v 4 . An argument favoring this assignment is the value of the effective quantum number of n* = 2.334, calculated as based on this assumption, which is very close to the average value of n* = 2.333 ± 0.030.…”

Section: The Experimental Datamentioning

confidence: 99%

“…Keeping this aim in mind, molecular systems e.g. ethylene and its various halogenated derivatives [1][2][3][4][5] and monohalogenated methanes [6] are being or have been investigated. Several of these studies [5,[7][8][9] showed the major importance of the localization and identification of neutral molecular states embedded in the ionization continua.…”

Section: Introductionmentioning

confidence: 99%

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About the vacuum UV photoabsorption spectrum of methyl fluoride (CH3F): the fine structure and its vibrational analysis

et al. 2000

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The vacuum UV photoabsorption spectrum of CH 3 F has been recorded between 7 and 24 eV and has been analyzed in detail. Broad and structureless peaks are observed over the entire photon energy range. They are all assigned to transitions to Rydberg states, members of series converging successively to the 2e -1 , 5a-1 and 1e -1 ionization limits. These features are underlying very long series of narrow and weak structures in the range of 10-13.2 eV. Through a continuum subtraction procedure, about 70 lines could clearly be identified. These have been assigned to long vibrational progressions belonging to Rydberg states corresponding to the 2e → 3p and 2e → 6s/5d configurations.

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Reliability of estimation of recombination energies of molecular radical cations by charge exchange and a test of the exoergicity rule

Youn

Choe

Kim

2003

Rapid Comm Mass Spectrometry

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Charge exchange occurring in a collision cell of a mass spectrometer was used previously to find the very long-lived excited electronic states of molecular cations generated by electron ionization. The underlying criterion in the method, called the exoergicity rule, was that only electronically exoergic and resonant processes have large cross sections at low collision energy. The validity of this rule has been checked in this work by estimating the recombination energies of some molecular ions based on the presence/absence of charge-exchange signals from gases with different ionization energies, and comparing these estimates with the literature values. It is concluded that a recombination energy can be estimated to within an upper limit uncertainty of 0.1 eV with this technique, which validates the exoergicity rule proposed previously.

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Photoelectron spectroscopy of vinylbromide and intramolecular dynamics of the ionic B̃ state

Cited by 22 publications

References 28 publications

The vacuum UV photoabsorption spectroscopy of vinyl fluoride (C2H3F): The vibrational fine structure and its analysis

The vacuum UV photoabsorption spectroscopy of vinyl fluoride (C2H3F): The vibrational fine structure and its analysis

About the vacuum UV photoabsorption spectrum of methyl fluoride (CH3F): the fine structure and its vibrational analysis

Reliability of estimation of recombination energies of molecular radical cations by charge exchange and a test of the exoergicity rule

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