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Density Functional Theory Predicts the Barriers for Radical Fragmentation in Solution

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journal contribution
posted on 18.03.2005, 00:00 by Edward D. Lorance, Kirstin Hendrickson, Ian R. Gould
N-Methoxypyridyl radicals formed by one-electron reduction of the corresponding cationic heterocycles undergo N−O bond cleavage. Experimental activation free energies for a series of these bond fragmentations are compared to corresponding barriers determined from electronic structure calculations. The DFT barriers agree well with those from experiment, being smaller than the latter values by an average value of ca. 1 kcal/mol, for rate constants varying over almost 3 orders of magnitude, or within ca. 3 kcal/mol over 8 orders of magnitude of rate constant. For a model compound, the B3PW91/6-31+G* hybrid density functional method is also found to be in good agreement with the MCSCF-MRMP2 method. One of the reactions is found by DFT to have no minimum for the reactant radical, consistent with a truly barrierless reaction.