title: Computational study of the reaction mechanism of the methylperoxy self-reaction.
abstract: To provide insight on the reaction mechanism of the methyperoxy (CH(3)O(2)•) self-reaction, stationary points on both the spin-singlet and the spin-triplet potential energy surfaces of 2(CH(3)O(2)•) have been searched at the B3LYP/6-311++G(2df,2p) level. The relative energies, enthalpies, and free energies of these stationary points are calculated using CCSD(T)/cc-pVTZ. Our theoretical results indicate that reactions on a spin-triplet potential energy surface are kinetically unfavorable due to high free energy barriers, while they are more complicated on the spin-singlet surface. CH(3)OOCH(3) + O(2)(1) can be produced directly from 2(CH(3)O(2)•), while in other channels, three spin-singlet chain-structure intermediates are first formed and subsequently dissociated to produce different products. Besides the dominant channels producing 2CH(3)O• + O(2) and CH(3)OH + CH(2)O + O(2) as determined before, the channels leading to CH(3)OOOH + CH(2)O and CH(3)O• + CH(2)O + HO(2)• are also energetically favorable in the self-reaction of CH(3)O(2)• especially at low temperature according to our results.
authors: College of Chemistry, Sichuan University, Chengdu, People's Republic of China.
authors: Yan-Ni
authors: YN
authors: Liang
authors: Jun
authors: J
authors: Li
authors: Quan-De
authors: QD
authors: Wang
authors: Fan
authors: F
authors: Wang
authors: Xiang-Yuan
authors: XY
authors: Li
mesh_terms: D005609:Free Radicals / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D005609:Free Radicals; D010545:Peroxides; C049375:perhydroxyl radical