A global search for the lowest energy isomer of C26

Abstract

The complete set of 2333 isomers of C(26) fullerene composed of square, pentagonal, hexagonal, and heptagonal faces together with some noncage structures is investigated at the Hartree-Fock and density functional theory (DFT) levels. For the singlet states, a nonclassical isomer C(26)-10-01 with a square embedded is predicted by the DFT method as the lowest energy isomer, followed by the sole classical isomer C(26)-00-01. Further explorations reveal that the electronic ground state of C(26)-10-01 is triplet state in C(s) symmetry, while that of C(26)-00-01 corresponds to its quintet in D(3h) symmetry. Both the total energies and nucleus independent chemical shift values at DFT level favor the classical isomer. It is found that both C(26)-00-01 and C(26)-10-01 possess high vertical electron affinity. The addition of electron(s) to C(26)-10-01 increases its aromatic character and encapsulation of Li atom into this cage is highly exothermic, indicating that it may be captured in the form of derivatives. To clarify the relative stabilities at elevated temperatures, the entropy contributions are taken into account based on the Gibbs free energy at the B3LYP/6-311+G( *) level. C(26)-10-01 behaves thermodynamically more stable than the classical isomer over a wide range of temperatures related to fullerene formation. The IR spectra of these two lowest energy isomers are simulated to facilitate their experimental identification.