Time-resolved resonance Raman study of the spectroscopy and kinetics of the Cl2- radical anion in aqueous solution

A. J. Hynes, P. H. Wine

Research output: Contribution to journalArticle

19 Scopus citations

Abstract

The resonance Raman spectrum of the chlorine molecular anion Cl 2- has been obtained using pulsed laser photolysis as a radical production method. The fundamental and nine overtone transitions are observed. Analysis of the vibrational progression gives the vibrational constants ωe = 277.0 ±0.3 cm-1 and ωeχe = 1.83 ±0.05 cm-1; these constants give an upper limit dissociation energy of 1.3 ± 0.1 eV (all errors are 1σ). Time-resolved resonance Raman spectroscopy has been employed to study the kinetics of Cl2- disproportionation. A disproportionation rate coefficient of (11 ±7) × 109 M-1 s-1 is obtained where the reported error includes 1σ precision and estimates of systematic errors. A resonance Raman detection limit for Cl2- of 5 × 10-6 M has been obtained.

Original languageEnglish (US)
Pages (from-to)3565-3572
Number of pages8
JournalThe Journal of Chemical Physics
Volume89
Issue number6
DOIs
StatePublished - Jan 1 1988
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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