This chapter deals with computational and theoretical support to fullerene/nanocarbon research needed for interpretations, rationalizations, and generalizations of experimental results. In particular, predictions of various nanocarbon stabilities, or even populations, based on quantum-chemical and statistical-mechanical methods, are surveyed. The calculations are, with respect to high temperatures in fullerene electric-arc syntheses, frequently based on the Gibbs energy. Considerable thermal effects on the relative isomeric and nonisomeric populations thus revealed in the theoretical treatments originate, on molecular level, in a complex interplay between rotational, vibrational, electronic, relative potential-energy, symmetry, and chirality factors. The considered treatments are built upon a presumption of the (inter-isomeric) thermodynamic equilibrium; however, some kinetic and catalytic aspects are also included. The survey is focused on empty fullerenes, metallofullerenes, clusterfullerenes, and nonmetal endohedrals. The covered quantum-chemical treatments are the semiempirical, ab initio Hartree-Fock, density-functional theory, and perturbation approaches. The calculations have already yielded a reasonable computation-observation agreement for the isomeric systems with empty C76 till C96 cages, and mostly also when applied to metallofullerenes. This relatively large tested set supports the belief in still wider applicability of the Gibbs-energy calculations to basically all classes of nanocarbons. This chapter is complementary to this volume chapter Theoretical Prediction of Fullerene Reactivity.
- DFT and ab initio calculations
- Gibbs-energy evaluations
- Isomeric and nonisomeric relative stabilities
- Kinetic control and catalysis
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)