Structures, stabilities, electronic, and optical properties of C64 fullerene isomers, anions (C  642− and C644−), metallofullerene Sc2@C64, and Sc2C2@C64

The 3465 classical isomers of C64 fullerene have been investigated by quantum chemical methods PM3, and the most stable isomers have been refined with HCTH/3‐21G//SVWN/STO‐3G, B3LYP/6‐31G(d)//HCTH/3‐21G, and B3LYP/6‐311G(d)//B3LYP/6‐31G(d) level. C64(D2:0003) with the lowest e55 (e55 = 2), the number of pentagon‐pentagon fusions, is predicted to be the most stable isomer and it is followed by the C64(Cs:0077) and C64(C2:0103) isomers within relative energy of 20.0 kcal/mol. C64(D2:0003) prevails in a wide temperature range according to energy analysis with entropy contribution at B3LYP/6‐31G(d) level. The simulated IR spectra and electronic spectra help to identify different fullerene isomers. All the hexagons in the isomers with e55 = 2 display local aromaticity. The relative stabilities of C64 isomers change with charging in ionic states. Doping also affects the relative stabilities of fullerene isomers as demonstrated by Sc2@C64(D2:0003) and Sc2@C64(Cs:0077). The bonding of Sc atoms with C64 elongates the CC bond of two adjacent pentagons and enhances the local aromaticity of the fullerene cages. Charging, doping, and derativization can be utilized to isolate C64 isomers through differentiating the electronic and steric effects. © 2008 Wiley Periodicals, Inc. J Comput Chem 2008

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