Electron capture detector response and dissociative electron attachment cross sections in chloroalkanes and chloroalkenes

Sathaporn Onanong, Paul D. Burrow, Steve D. Comfort, Patrick J. Shea

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Electron capture detectors (ECDs) are widely used in gas chromatography to detect electronegative compounds. In this work, we examine the connections between the ECD response and the cross sections for dissociative electron attachment (DEA) determined from low energy electron beam studies in the chloroalkane family, stressing in particular the role of temporary anion state energies. We show that attachment rate coefficients computed from these cross sections are well correlated with ECD response, and that the latter decreases exponentially with increasing energies of the lowest anion states. ECD measurements are also carried out in monochloroalkanes substituted with unsaturated ethenyl and phenyl moieties, and the response is shown to depend strongly on the mixing between the unsaturated π* and the C-Cl σ* temporary anions as exhibited by the vertical attachment energies (VAEs) of these states. The results show good correlations between the chloroalkene and phenyl chloride ECD responses and the VAEs for the mixed states.

Original languageEnglish (US)
Pages (from-to)4363-4368
Number of pages6
JournalJournal of Physical Chemistry A
Volume110
Issue number13
DOIs
StatePublished - Apr 6 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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