A Quantum Mechanical MP2 Study of the Electronic Effect of Nonplanarity on the Carbon Pyramidalization of Fullerene...

Among C₆₀'s diverse functionalities, its potential application in CO₂ sequestration has gained increasing interest. However, the processes involved are sensitive to the molecule's electronic structure, aspects of which remain debated and require greater precision. To address this, we performed structural optimization of fullerene C₆₀ using the QM MP2/6-31G* method. The nonplanarity of the optimized icosahedron is characterized by two types of dihedral angles: 138° and 143°. The 120 dihedrals of 138° occur between two hexagons intersecting at C-C bonds of 1.42 Å, while the 60 dihedrals of 143° are observed between hexagons and pentagons at C-C bonds of 1.47 Å. NBO analysis reveals less pyramidal sp^1.78 hybridization for carbons at the 1.42 Å bonds and more pyramidal sp^2.13 hybridization for the 1.47 Å bonds. Electrostatic potential charges range from -0.04 a.u. to 0.04 a.u. on the carbon atoms. Second-order perturbation analysis indicates that delocalization interactions in the C-C bonds of 1.42 Å (143.70 kcal/mol) and 1.47 Å (34.98 kcal/mol) are 22% and 38% higher, respectively, than those in benzene. MP2/Def2SVP calculations yield a correlation energy of 13.49 kcal/mol per electron for C₆₀, slightly higher than the 11.68 kcal/mol for benzene. However, the results from HOMO-LUMO calculations should be interpreted with caution. This study may assist in the rational design of fullerene C₆₀ derivatives for CO₂ reduction systems.