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Russian Journal of General Chemistry

, Volume 85, Issue 11, pp 2596–2604 | Cite as

Discrimination of stereoisomers of 2-chlorovinyldichloroarsine and bis(2-chlorovinyl)chloroarsine from the data of negative ion mass spectrometry and quantum-chemical simulation

  • R. V. KhatymovEmail author
  • M. V. Ivanova
  • A. G. Terentyev
  • I. V. Rybal’chenko
Article

Abstract

Chromato–mass spectrometry has been applied to investigate technical lewisite containing α- and β-isomers, each containing the respective stereoisomers. The mass spectra of positive ions of the stereoisomers have been practically identical, whereas substantial differences have been observed in the negative ion mass spectra. Using quantum-chemical simulation at the B3LYP/6-311+G(d,p) level, the relative stability of the isomers, bonds dissociation energy, electron affinity, and ionization energy have been estimated. The formation of characteristic negative ions from the cis-isomer of α-lewisite and their absence for the trans-isomer is shown to be driven by the steric factors affecting the rearrangement processes.

Keywords

lewisite resonance electron-capture negative ion mass spectrometry fragmentation rearrangement dissociation energy 

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Copyright information

© Pleiades Publishing, Ltd. 2015

Authors and Affiliations

  • R. V. Khatymov
    • 1
    Email author
  • M. V. Ivanova
    • 2
  • A. G. Terentyev
    • 2
  • I. V. Rybal’chenko
    • 3
    • 4
  1. 1.Institute of Molecule and Crystal PhysicsUfa Research Center of Russian Academy of SciencesUfaRussia
  2. 2.Timoshenko Military Academy of Radiation, Chemical and Biological ProtectionMinistry of Defense of Russian FederationKostromaRussia
  3. 3.27 Scientific Center of Ministry of Defense of Russian FederationMoscowRussia
  4. 4.Kostroma State Technological UniversityKostromaRussia

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