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

4 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

Fingerprint

Decomposition
Decompose
Potential Energy Surface
Phenol
Potential energy surfaces
Reaction Rate
Rate Constant
Phenols
Reaction rates
Migration
Rate constants
Molecules
Dependent
thiophenol
Temperature

Keywords

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

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

Theoretical study on the unimolecular decomposition of thiophenol. / Al-Muhtaseb, Ala'A H.; Altarawneh, Mohammednoor; Almatarneh, Mansour H.; Poirier, Raymond A.; Assaf, Niveen W.

In: Journal of Computational Chemistry, Vol. 32, No. 12, 09.2011, p. 2708-2715.

Research output: Contribution to journalArticle

Al-Muhtaseb, AAH, Altarawneh, M, Almatarneh, MH, Poirier, RA & Assaf, NW 2011, 'Theoretical study on the unimolecular decomposition of thiophenol', Journal of Computational Chemistry, vol. 32, no. 12, pp. 2708-2715. https://doi.org/10.1002/jcc.21852
Al-Muhtaseb, Ala'A H. ; Altarawneh, Mohammednoor ; Almatarneh, Mansour H. ; Poirier, Raymond A. ; Assaf, Niveen W. / Theoretical study on the unimolecular decomposition of thiophenol. In: Journal of Computational Chemistry. 2011 ; Vol. 32, No. 12. pp. 2708-2715.
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