The mechanism of the ozonolysis on the surface of C fullerene: the electron localizability indicator study.

The formation of CO from CO monomolozonide is a three-step process with the isomer dependent last step leading either to c,c-CO epoxide or d,d-CO oxidoannulene. The process involves the open intermediate (first O-O then C-C/C-C bonds broken), oxidoannulene-like structure intermediate (new C-O/C-O bond formed) and finally the oxide product. On the formation of c,c-CO isomer, the final release of O is followed by the restoration of C-C bond, which stabilizes the product. Neither C-C bond is restored nor the total energy essentially lowered upon d,d-CO formation. At all steps of the studied process, the four CC bonds adjacent to C-C or C-C bond, respectively, play a crucial role donating or withdrawing the necessary electron density. C(O)O products, with O bridging one of the bonds adjacent to the parent C-C/C-C one, may compete with the oxide products. The OO bond in such structures is weak as suggested by its low electron population. For both c,c-CO and d,d-CO, the shape of the potential energy surfaces (0 K) and the related, reported earlier, room temperature-free energy surfaces differ. Graphical abstract.