Fullerenes: formation, stability, and reactivity

Ab initio, density functional theory and semiempirical methods have been extensively used in the study of fullerenes since its discovery 25 years ago. Here, we review the most recent theoretical studies on formation mechanisms, stability, and reactivity of empty and endohedral fullerenes. We have focused on medium-large fullerenes reporting the relevance of the temperature in the stability of fullerene, the role of the electron transfer in the stabilization of a particular cage in endohedral metallofullerenes (EMFs), and the importance of carbon hybridation in the reactivity of empty fullerenes and EMFs. Finally, we show the essential stages in the formation of a fullerene (nucleation, cage growth, and cage closure) within the so-called the 'shrinking hot giant' road. (C) 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 350-367 DOI: 10.1002/wcms.21