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

Abstract

The ground state of odd-N polyynic oligomers C_{N}H_{2} 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 DFT 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.