Abstract
The mechanisms and kinetics studies of the OH radical with alkyl hydroperoxides CH(3)OOH and CH(3)CH(2)OOH reactions have been carried out theoretically. The geometries and frequencies of all the stationary points are calculated at the UBHandHLYP/6-311G(d,p) level, and the energy profiles are further refined by interpolated single-point energies method at the MC-QCISD level of theory. For two reactions, five H-abstraction channels are found and five products (CH(3)OO, CH(2)OOH, CH(3)CH(2)OO, CH(2)CH(2)OOH, and CH(3)CHOOH) are produced during the above processes. The rate constants for the CH(3)OOH/CH(3)CH(2)OOH + OH reactions are corrected by canonical variational transition state theory within 250-1500 K, and the small-curvature tunneling is included. The total rate constants are evaluated from the sum of the individual rate constants and the branching ratios are in good agreement with the experimental data. The Arrhenius expressions for the reactions are obtained.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
