Relative and absolute bond dissociation energies of sodium cation-alcohol complexes determined using competitive collision-induced dissociation experiments

Jay Amicangelo, P. B. Armentrout

Research output: Contribution to journalArticle

8 Scopus citations

Abstract

Absolute (R1OH)Na+-(R2OH) and relative Na+-(ROH) bond dissociation energies are determined experimentally by competitive collision-induced dissociation of (R1OH)Na +(R2OH) complexes with xenon in a guided ion beam mass spectrometer. The alcohols examined include ethanol, 1-propanol, 2-propanol, n-butanol, iso-butanol, sec-butanol, and tert-butanol, which cover a range in Na+ affinities of only 11 kJ/mol. Dissociation cross sections for formation of Na+(R1OH) + R2OH and Na +(R2OH) + R1OH are simultaneously analyzed with a model that uses statistical theory to predict the energy dependent branching ratio. The cross section thresholds thus determined are interpreted to yield the 0 K (R1OH)Na+-(R2OH) bond dissociation energies and the relative 0 K Na+-(ROH) binding affinities. The relative binding affinities are converted to absolute 0 K Na+-(ROH) binding energies by using the absolute bond energy for Na+-C 2H5OH determined previously in our laboratory as an anchor value. Comparisons are made to previous experimental and theoretical Na +-(ROH) thermochemistry from several sources. The absolute (R 1OH)Na+-(R2OH) bond dissociation energies were also calculated using quantum chemical theory at the MP2(full)/6-311+G(2d,2p)// MP2(full)/6-31G(d) level (corrected for zero-point energies and basis set superposition errors) and are generally in good agreement with the experimentally determined values.

Original languageEnglish (US)
Pages (from-to)45-54
Number of pages10
JournalInternational Journal of Mass Spectrometry
Volume301
Issue number1-3
DOIs
StatePublished - Mar 30 2011

All Science Journal Classification (ASJC) codes

  • Instrumentation
  • Condensed Matter Physics
  • Spectroscopy
  • Physical and Theoretical Chemistry

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