In:
Journal of Theoretical and Computational Chemistry, World Scientific Pub Co Pte Ltd, Vol. 08, No. 01 ( 2009-02), p. 119-142
Abstract:
The complex potential energy surface for the self-reaction of CH 2 ClO 2 radicals, including 12 intermediates, 33 interconversion transition states, and 21 major dissociation products, was theoretically probed at the CCSD(T)/cc-pVDZ//B3LYP/6-311G(2d,2p) level of theory. The geometries and relative energies for various stationary points were determined. Based on the calculated CCSD(T)/cc-pVDZ potential energy surface, the possible mechanism for the studied system was proposed. It is shown that the most feasible channels are those leading to 2 2 CH 2 ClO + 3 O 2 , 2 CH 2 ClO + 2 HO 2 + CHClO , 2 CH 2 ClO + HCl + 2 CH(O)O 2 , 2 CH 2 ClO + 3 O 2 + 2 Cl + CH 2 O , and p,s,o- CH 2 ClOOOCl + CH 2 O with the energy barriers of 5.6, 11.8, 12.4, 12.4, and 13.5 kcal/mol, respectively. Their mechanisms are that CH 2 ClO 2 and CH 2 ClO 2 form a tetroxide intermediate first, then the intermediate dissociates to yield the productions or through multi-steps reactions to produce the final products.
Type of Medium:
Online Resource
ISSN:
0219-6336
,
1793-6888
DOI:
10.1142/S0219633609004587
Language:
English
Publisher:
World Scientific Pub Co Pte Ltd
Publication Date:
2009
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