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Figure 6 represents the spin densities derived from the AIM definition. However, the results obtained by using the NPA spin density populations are essentially identical, as the NPA and AIM charges are linearly related with a correlation coefficient of 0.98. Details are provided in the Supporting Information.
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3CO. Consequently, these structures do not represent any delocalization not already present before hydrogen atom abstraction takes place, and so they are ignored in this analysis.
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2 hybridization) implies that structure 3a (which strictly speaking requires sp hybridization at C) is not rigorously correct. The alternative structure 3e below corrects this problem, and can be thought of as a substitute for 3a. The replacement of 3a with 3e does not affect predictions of where spin density will be located, and merely represents polarization of the C-N π electrons, and so this issue is not pursued further here. (Formula Presented)
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2NCH. The replacement of 4a with 4d does not affect predictions of where spin density will be located, and merely represents polarization of the C-N π electrons, and so this issue is not pursued further here. (Formula Presented)
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Subtractions were performed while holding the geometries of the separate fragments constant. Control calculations, described in the Supporting Information, showed that little error was introduced by the required geometric constraints.
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