Kinetics of the methoxy radical decomposition reaction: Theory and experiment

M. Page*, Ming-Chang Lin, Yisheng He, T. K. Choudhury

*此作品的通信作者

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53 引文 斯高帕斯(Scopus)

摘要

The rate constant for the unimolecular decomposition of the methoxy radical, CH3O + M → CH2O + H + M, is determined both theoretically and experimentally. In the theoretical calculations, potential energy surface information is obtained from ab initio multiconfiguration SCF and multireference configuration interaction calculations using basis sets of up to triple-ζ plus polarization quality. The zero point corrected forward and reverse barriers are calculated to be 25.6 and 8.0 kcal/mol, respectively. RRKM rate calculations are performed incorporating a quantum correction due to tunneling through an Eckart barrier fit to represent the MRCI/TZP energetics and the shape of the MC-SCF/DZP vibrationally adiabatic potential energy curve in the saddle point region. The calculated values compare closely with experimental data derived from kinetic modeling of CO formation rates measured in the thermal decomposition of methyl nitrite at 550-700 K in a static cell and at 1060-1620 K in shock waves.

原文English
頁(從 - 到)4404-4408
頁數5
期刊Journal of Physical Chemistry
93
發行號11
DOIs
出版狀態Published - 1 1月 1989

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