文摘
Highest occupied molecular orbital–lowest unoccupied molecular orbital (H-L) energy gaps govern the chemical stabilities of molecules. Molecules with larger H-L gaps are more inert to chemical reactions and thus more experimentally separable. In this sense, H-L gaps play a more important role than energies of formation in determining the structures of the fullerenols that can be experimentally isolated. However, previous structural predictions for fullerenols are mainly based on energies. Recently, we proposed a rule of chemical stability for multiple addition products of fullerenes and endohedral metallofullerenes. In this study, we implement this rule into a computer program and use it to automatically determine large-energy-gap structures for C60 and C82 fullerenols. C60(OH)n (n = 12–48) and C2v(9)-C82(OH)x (x = 14–58) fullerenols have been studied using this program. All the structures determined have H-L gaps larger than those predicted previously. Some of the structures simultaneously have even more favorable thermodynamic stabilities than the previously predicted structures. Therefore, the results we present here provide an improved description for the structures of fullerenols.