First ab initio and density functional study on the structure, bowl-to-bowl inversion barrier, and vibrational spectra of the elusive C-3v-symmetric buckybowl: Sumanene, C21N12

The synthetically elusive C-3 upsilon symmetric sumanene (C21H12), a key st ructural motif of C-60, was subjected to a detailed computational study, ex ploring the structure, bowl-to-bowl inversion dynamics, vibrational spectra , and some other physicochemical properties. Hartree-Fock (HF), pure (BLYP, BP86, and BPW91), and hybrid density functional (B3LYP, B3P86, and B3PW91) calculations were done with an array of basis sets (STO-3G, 3-21G, 6-31G*, 6-31G**, 6-311G*, 6-311G**, 6-311+G*, 6-311++G*, cc-pVDZ, and cc-pVTZ). Th e effect of a basis set higher than double-zeta quality and the inclusion o f dynamic correlation on the geometry and bowl-to-bowl inversion barrier wa s insignificant. The B3LYP or HF method with the cc-pVDZ or 6-311G* basis s et gave satisfactory results. The previously computed modified neglect of d iatomic overlap (MNDO) value of 24.2 kcal/mol for the bowl-to-bowl inversio n was found to be too high, and a revised value of 16.9 kcal/mol was obtain ed by the B3LYP/cc-pVTZ//B3LYP/cc-pVDZ method. Consequently, the computed r esults indicate that sumanene (2) is not locked in the bowl geometry and th at a definitive bowl-to-bowl inversion should exist at room temperature. Th e highest level of theory used in the study (B3LYP/6-311G**) yields values of 1.14 Angstrom, 2.45 D, and 98.8 degrees for the bowl depth, dipole momen t, and pi -orbital axis vector angle at the hub carbon for sumanene, respec tively. Interesting temperature dependency of inversion dynamics is predict ed near room temperature.