Structures and Electronic Properties of C56Cl8 and C56Cl10 Fullerene Compounds

Abstract

AbstractStimulated by the recent observation of the first C56Cl10 chlorofullerene (Science, 2004, 304, 699), we performed a systematic density functional study of the structures and properties of C56Cl10 and related compounds. The fullerene derivatives C56Cl8 and C56Cl10 based on the parent fullerene C56(C2v:011), rather than those from the most stable C56 isomer with D2 symmetry, are predicted to possess the lowest energies, and they are highly aromatic. Further investigations show that the heats of formation of the C56Cl8 and C56Cl10 fullerene derivatives are highly exothermic, that is, −48.59 and −48.89 kcal mol−1 per Cl2 (approaching that of C50Cl10), suggesting that adding eight (or ten) Cl atoms releases much of the strain of pure C56(C2v:011) fullerene and leads to highly stable derivatives. In addition, C56Cl8 and C56Cl10 possess large vertical electron affinities, especially for C56Cl8 with value of 3.20 eV, which is even larger than that (3.04 eV) of C50Cl10, indicating that they are potential good electron acceptors with possible photonic/photovoltaic applications. Finally, the 13C NMR chemical shifts and infrared spectra of C56Cl8 and C56Cl10 are simulated to facilitate future experimental identification.