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Various reaction pathways on the potential energy surface for the ClCO + NO 2 , radicals which are both known to be upper atmosphere pollutants, were investigated at the B3LYP level of theory using the 6-311G(d) and 6-311+G(3df) basis sets. The energetics were refined with G3//B3LYP and CBS-QB3 calculations. The following reaction channels between the two are the most probable: (i) the formation of ClNO + CO 2 or ClON + CO 2 via cis – trans ClC(O)ONO or cis – cis ClC(O)ONO intermediates, respectively, and (ii) the formation of the low-lying adduct trans – trans ClC(O)ONO. The other adduct ClC(O)NO 2 is calculated to lie about 20 kcal mol −1 higher in energy than trans – trans ClC(O)ONO. Thus, trans – trans ClC(O)ONO can be considered to be a sink for ClCO radical on the ground-state surface. |
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