A comparative ab initio study of neutral and charged kink solitons on conjugated carbon chains

Abstract

The ground state of odd-N polyynic oligomers CNH2 features kink solitons in carbon-carbon bond-length alternation (BLA) patterns. We perform a systematic first-principles computational study of neutral and singly charged kinks in long oligomers addressing relationships between BLA patterns, electron energy gaps, and accompanying distributions of spin and charge densities, both in vacuum and in the screening solvent environment. A quantitative comparison is made of the results derived with four different ab initio methods: from pure density-functional theory to pure Hartree–Fock (HF) and including two popular hybrid density functionals, B3LYP and BHandHLYP. A clear correlation is demonstrated between the derived spatial extent of kinks and the amount of HF exchange used in the functionals. For charged kinks, we find a substantial difference in the behavior of charge and spin densities.