Theoretical study of the O(3P) + allene reaction

B. L. Hammond, S. Y. Huang, W. A. Lester, M. Dupuis

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Ab initio complete active space SCF calculations have been performed to determine the structures and energetics of the electrophilic addition of O(3P) to aliene (propadiene). The long-established channel for this reaction has been O-atom attack of the central carbon atom (CCA). However, recent experimental studies have suggested that terminal carbon attack (TCA) is a significant process. In this study the classical barrier height for the CCA channel was found to be only 1.8 kcal/mol lower than that for the TCA channel. In addition, the triplet diradical species and the experimentally observed product of the TCA channel, allenyloxy radical, are characterized. Allenyloxy radical is predicted to have low-lying near-IR and UV transitions to electronic excited states 0.525 and 3.70 eV above the ground state. Similar transitions for the analogous vinoxy radical have previously been predicted theoretically and confirmed experimentally.

Original languageEnglish
Pages (from-to)7969-7972
Number of pages4
JournalJournal of physical chemistry
Volume94
Issue number20
DOIs
Publication statusPublished - Jan 1 1990

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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