Bond Length Alternation and Energy Band Gap of Polyyne

The bond length alternation (BLA) and energy band gap of polyyne are investigated by various first-principles theories, including Hartree−Fock, MP2, hybrid, and nonhybrid density functional theories. Both solid-state calculations utilizing periodic boundary conditions on polymers and molecular quantum mechanical calculations on extra-long oligomers were performed with consistent results. By validation on similar linear conjugated polymers, polyacetylene and polydiacetylene, the combination of hybrid-DFT schemes, B3LYP//BHandHLYP or B3LYP//KMLYP, is shown to give the best predictions for both geometry and band gap of polyyne based on available experimental data. We conclude that the best estimate of the BLA of polyyne is about 0.13 Å and that of the band gap is about 2.2 eV.