Reaction mechanisms and kinetics of the elimination processes of 2-chloroethylsilane and derivatives: A DFT study using CTST, RRKM, and BET theories
The thermal decomposition kinetics of 2-chloroethylsilane and derivatives in the gas phase has been studied computationally using density functional theory, along with various exchange-correlation functionals (UM06-2x and ωB97XD) and the aug-cc-pVTZ basis set. The calculated energy profile has been...
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Published in | Chemical physics Vol. 485-486; pp. 140 - 148 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Elsevier B.V
01.03.2017
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Subjects | |
Online Access | Get full text |
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Summary: | The thermal decomposition kinetics of 2-chloroethylsilane and derivatives in the gas phase has been studied computationally using density functional theory, along with various exchange-correlation functionals (UM06-2x and ωB97XD) and the aug-cc-pVTZ basis set. The calculated energy profile has been supplemented with calculations of kinetic rate constants under atmospheric pressure and in the fall-off regime, using transition state theory (TST) and statistical Rice–Ramsperger–Kassel–Marcus (RRKM) theory. Activation energies and rate constants obtained using the UM06-2x/aug-cc-pVTZ approach are in good agreement with the experimental data. The decomposition of 2-chloroethyltriethylsilane species into the related products [C2H4+Et3SiCl] is characterized by 6 successive structural stability domains associated to the sequence of catastrophes C8H19SiCl: 6-C†FCC†[FF]-0: C6H15SiCl+C2H4. Breaking of Si–C bonds and formation of Si–Cl bonds occur in the vicinity of the transition state. |
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ISSN: | 0301-0104 |
DOI: | 10.1016/j.chemphys.2017.01.009 |