Priyakumar, U. Deva ; Sastry, G. Narahari (2001) First ab initio and density functional study on the structure, bowl-to-bowl inversion barrier, and vibrational spectra of the elusive C3v-Symmetric Buckybowl: sumanene, C21H12 The Journal of Physical Chemistry A, 105 (18). pp. 4488-4494. ISSN 1089-5639
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Official URL: http://pubs.acs.org/doi/abs/10.1021/jp0037549
Related URL: http://dx.doi.org/10.1021/jp0037549
Abstract
The synthetically elusive C3v symmetric sumanene (C21H12), a key structural motif of C60, was subjected to a detailed computational study, exploring 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). The effect of a basis set higher than double-ζ quality and the inclusion of dynamic correlation on the geometry and bowl-to-bowl inversion barrier was insignificant. The B3LYP or HF method with the cc-pVDZ or 6-311G* basis set gave satisfactory results. The previously computed modified neglect of diatomic overlap (MNDO) value of 24.2 kcal/mol for the bowl-to-bowl inversion was found to be too high, and a revised value of 16.9 kcal/mol was obtained by the B3LYP/cc-pVTZ//B3LYP/cc-pVDZ method. Consequently, the computed results indicate that sumanene (2) is not locked in the bowl geometry and that a definitive bowl-to-bowl inversion should exist at room temperature. The highest level of theory used in the study (B3LYP/6-311G**) yields values of 1.14 Å, 2.45 D, and 98.8° for the bowl depth, dipole moment, and π-orbital axis vector angle at the hub carbon for sumanene, respectively. Interesting temperature dependency of inversion dynamics is predicted near room temperature.
Item Type: | Article |
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Source: | Copyright of this article belongs to American Chemical Society. |
ID Code: | 106316 |
Deposited On: | 02 Aug 2017 07:02 |
Last Modified: | 02 Aug 2017 07:10 |
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