Dispersion interaction in hydrogen-chain models

Abstract

We have investigated the dispersion interaction in hydrogen chain models via density functional theory-based symmetry-adapted perturbation theory using the asymptotically corrected PBE0 energy functional. The quasimetallic and the insulating prototype systems were chosen to be hydrogen chains with equally and alternately spaced H2 units, respectively. The dependence of the dispersion energy on the chain length for quasimetallic and insulating cases has been determined for two chains arranged either in pointing or in parallel geometries. The results are compared with those previously calculated from a continuum coupled-plasmon approach [Phys. Rev. B 77, 075436 (2008)]. The interaction energy has also been modeled by pairwise summations over short fragments of the chains, demonstrating the failure of the additivity principle for the quasimetallic case, while confirming that the additivity is a qualitatively reasonable hypothesis for the insulating case.