TY - JOUR
T1 - Theoretical study on the unimolecular decomposition of thiophenol
AU - Al-Muhtaseb, Ala'A H.
AU - Altarawneh, Mohammednoor
AU - Almatarneh, Mansour H.
AU - Poirier, Raymond A.
AU - Assaf, Niveen W.
PY - 2011/9
Y1 - 2011/9
N2 - 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.
AB - 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.
KW - BB1K
KW - DFT
KW - potential energy surface
KW - reaction rate constants
KW - thiophenol
KW - unimolecular decomposition
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U2 - 10.1002/jcc.21852
DO - 10.1002/jcc.21852
M3 - Article
C2 - 21647931
AN - SCOPUS:79959765961
SN - 0192-8651
VL - 32
SP - 2708
EP - 2715
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
IS - 12
ER -