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Theoretical kinetic study of the CH 3 Br + OH atmospheric system

Chemical Physics, ISSN: 0301-0104, Vol: 324, Issue: 2, Page: 591-599
2006
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Ab initio calculations were conducted for both reaction pathways of the CH 3 Br and OH system. Geometry optimization and vibrational frequencies analysis were performed for reactants, pre-reaction complex, transition states, post-reaction complex and products at the MP2(full)/6-311+G(d,p), MP2(full)/6-311+G(3df,2pd) and MP2(full)/cc-pVTZ levels of theory. Energetic results were further refined by CCSD(T,full) calculations, using optimized geometric parameters of the MP2(full)/cc-pVTZ level, i.e., CCSD(T,full)/cc-pVTZ//MP2(full)/cc-pVTZ. Based on MP2(full)/cc-pVTZ and CCSD(T,full)/cc-pVTZ//MP2(full)/cc-pVTZ data, rate constants were deduced in the 200–2000 K temperature range, using conventional transition state theory and Wigner tunneling correction. Calculated rate constants, including tunneling corrections, were found to be in excellent agreement with experimental results.

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