Theoretical study on the unimolecular decomposition of thiophenol

Ala'A H. Al-Muhtaseb, Mohammednoor Altarawneh, Mansour H. Almatarneh, Raymond A. Poirier, Niveen W. Assaf

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The potential energy surface for the unimolecular decomposition of thiophenol (C 6H 5SH) is mapped out at two theoretical levels; BB1K/GTlarge and QCISD(T)/6-311+G(2d,p)//MP2/6-31G(d,p). Calculated reaction rate constants at the high pressure limit indicate that the major initial channel is the formation of C 6H 6S at all temperatures. Above 1000 K, the contribution from direct fission of the Si-H bond becomes important. Other decomposition channels, including expulsion of H 2 and H 2S are of negligible importance. The formation of C 6H 6S is predicted to be strong-pressure dependent above 900 K. Further decomposition of C 6H 6S produces CS and C 5H 6. Overall, despite the significant difference in bond dissociation, i.e., 8-9 kcal/mol between the Si-H bond in thiophenol and the Oi-H bond in phenol, H migration at the ortho position in the two molecules represents the most accessible initial channel.

Original languageEnglish
Pages (from-to)2708-2715
Number of pages8
JournalJournal of Computational Chemistry
Volume32
Issue number12
DOIs
Publication statusPublished - Sep 2011

Keywords

  • BB1K
  • DFT
  • potential energy surface
  • reaction rate constants
  • thiophenol
  • unimolecular decomposition

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

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