Mass spectrometry of resonance capture of electrons and photo-electron spectroscopy of molecules of ethylene oxide, ethylene sulfide, and their derivatives

Воробьев, А. С.; Furlei, I. I.; Sultanov, A. Sh.; Khvostenko, V. I.; Leplyanin, G. V.; Derzhinskii, A. R.; Толстиков, Г. А.

doi:10.1007/bf00978424

Cited by 11 publications

(13 citation statements)

References 7 publications

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“…The experimental results obtained in the present work on the valence electronic structure of epichlorohydrin are summarized in Table 1. These results can be compared with those obtained by other authors, [24][25][26][27] which are also reported in the same table. The first experimental study of epichlorohydrin by PES 25 provided the vertical IE values as observed by 21.2 eV ionizing photons (HeI line source).…”

Section: Electronic Structure Assignmentsupporting

confidence: 75%

“…A third and more recent investigation of the electronic structure of molecules structurally related to oxirane 27 supplies information on the five outermost PE bands of epichlorohydrin and their assignment. Four IE values have been measured in the first group of PE bands and a fifth value is measured at higher energies, namely at 13.51 eV.…”

Section: Electronic Structure Assignmentmentioning

confidence: 99%

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The valence electronic structure and conformational flexibility of epichlorohydrin

Stranges

Alagia

Decleva

et al. 2011

Phys. Chem. Chem. Phys.

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The electronic structure of epichlorohydrin is investigated in the whole valence region by a combined experimental and theoretical study. The issue of controversial assignments of the molecular electronic structure is here addressed. Photoelectron spectra (PES) and Threshold Photoelectron spectra (TPES) of room temperature molecules in the gas phase are recorded. Geometries and energies of the stable conformers due to internal rotation of the C-C-C-Cl dihedral angle, gauche-II (g-II), gauche-I (g-I), and cis, are calculated, and the effect of the conformational flexibility on the photoionization energetics is studied by DFT and 2h-1p Configuration Interaction (CI) methods. Strong breakdown of the Koopmans Theorem (KT) is obtained for the four outermost ionizations, which are further investigated by higher level ab initio calculations. The full assignment of the spectrum is put on a firm basis by the combination of experimental and theoretical results. The orbital composition from correlated calculations is found closer to the DFT orbitals, which are then used to analyze the electronic structure of the molecule. The Highest Occupied Molecular Orbital (HOMO) and HOMO--2 are n(O)/n(Cl) mixed orbitals. The nature of each valence MO is generally preserved in all the conformers, although the magnitude of the n(O)/n(Cl) mixing in HOMO and HOMO--2 varies to some extent with the C-C-C-Cl dihedral angle. The low energy part of the HOMO PE band is predicted to be substantially affected by the conformational flexibility, as experimentally observed in the spectra. The rest of the spectrum is described in terms of the dominant conformer g-II, and a good agreement between experiment and theory is found. The inner-valence PE spectrum is characterized by satellite structures, due to electron correlation effects, which are interpreted by means of 2h-1p CI calculations.

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Section: Electronic Structure Assignmentsupporting

confidence: 75%

Section: Electronic Structure Assignmentmentioning

confidence: 99%

The valence electronic structure and conformational flexibility of epichlorohydrin

Stranges

Alagia

Decleva

et al. 2011

Phys. Chem. Chem. Phys.

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“… a Hydrogen atom abstraction reaction efficiency = second-order hydrogen atom abstraction rate constant / collision rate constant (k exp /k coll ). b Calculated at the B3LYP/aug-cc-pVTZ//B3LYP/cc-pVTZ level of theory. c Reference 55. d Reference 56. …”

Section: Figures and Tablesmentioning

confidence: 99%

Gas-Phase Reactivity of Protonated 2-, 3-, and 4-Dehydropyridine Radicals Toward Organic Reagents

et al. 2009

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In order to explore the effects of the electronic nature of charged phenyl radicals on their reactivity, reactions of the three distonic isomers of ndehydropyridinium cation (n = 2, 3 or 4) have been investigated in the gas phase by using Fourier-transform ion cyclotron resonance mass spectrometry. All three isomers react with cyclohexane, methanol, ethanol and 1-pentanol exclusively via hydrogen atom abstraction, and with allyl iodide mainly via iodine atom abstraction, with a reaction efficiency ordering: 2 > 3 > 4. The observed reactivity ordering correlates well with the calculated vertical electron affinities of the charged radicals (i.e., the higher the vertical electron affinity, the faster the reaction). Charged radicals 2 and 3 also react with tetrahydrofuran exclusively via hydrogen atom abstraction, but the reaction of 4 with tetrahydrofuran yields products arising from nonradical reactivity. The unusual reactivity of 4 is likely to result from the contribution of an ionized carbenetype resonance structure that facilitates nucleophilic addition to the most electrophilic carbon atom (C-4) in this charged radical. The influence of such a resonance structure on the reactivity of 2 is not obvious, and this may be due to stabilizing hydrogen-bonding interactions in the transition states for this molecule. Charged radicals 2 and 3 abstract a hydrogen atom from the substituent in both phenol and toluene, but 4 abstracts a hydrogen atom from the phenyl ring -a reaction that is unprecedented for phenyl radicals. Charged radical 4 reacts with tert-butyl isocyanide mainly by hydrogen cyanide (HCN) abstraction while CN abstraction is the principal reaction for 2 and 3. The different reactivity observed for 4 (compared to 2 and 3) is likely to result from different charge and spin distributions of the reaction intermediates for these charged radicals.

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“…Additionally, it is noted that, while our TOF mass spectrometric experiments failed to detect the parent cation of chloropropylene oxide, the IE of this molecule was successfully measured by PES. [3][4][5] This is due to the fact that, in the PES experiments, we need only to detect the photoelectron corresponding to the formation of the parent cation, and no measurement is made on the parent cation itself.…”

Section: Resultsmentioning

confidence: 99%

“…The ionization energy (IE) of chloropropylene oxide was measured by various groups using photoelectron spectroscopy. [3][4][5] The appearance energies (AEs) of the principal cations in the mass spectra of chloropropylene oxide were obtained employing electron impact (EI) technique. 6 Moreover, probable dissociation processes were given.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Studies of the VUV Photoionization of Chloropropylene Oxide

Liu¹,

Li²,

Wu³

et al. 2001

J. Phys. Chem. A

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The photoionization and dissociative photoionization of chloropropylene oxide have been studied both experimentally and theoretically. In experiments, photoionization efficiency spectra for ions C3H5O+, CHO+, C2H4 +, C2H3 +, C2H2 +, CH3 +, and CH2OH+ were obtained. Theoretically, the energetics of the dissociative photoionizations were examined by ab initio Gaussian-3 calculations. The computational results are useful in our attempt to establish the dissociative photoionization channels of chloropropylene oxide. These proposed channels include six simple bond cleavage reactions as well as a reaction involving intermediates and transition structures. The agreement between experimental and computational dissociation energies or barriers ranges from fair to excellent.

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Mass spectrometry of resonance capture of electrons and photo-electron spectroscopy of molecules of ethylene oxide, ethylene sulfide, and their derivatives

Cited by 11 publications

References 7 publications

The valence electronic structure and conformational flexibility of epichlorohydrin

The valence electronic structure and conformational flexibility of epichlorohydrin

Gas-Phase Reactivity of Protonated 2-, 3-, and 4-Dehydropyridine Radicals Toward Organic Reagents

Experimental and Theoretical Studies of the VUV Photoionization of Chloropropylene Oxide

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