Hybrid functional analysis of porous coordination polymers Cu[Cu(pdt)$_{2}$] and Cu[Ni(pdt)$_{2}$]

TL;DR

This study uses hybrid functional methods to analyze the electronic and excitonic properties of two porous coordination polymers, revealing their degenerate p-type semiconducting nature and strong correlation effects in Cu 3d electrons.

Contribution

It applies a combination of hybrid DFT, G0W0, and Bethe-Salpeter approaches to characterize the electronic structure and excitonic effects in these materials, highlighting the importance of partial self-interaction correction.

Findings

Materials are degenerate p-type semiconductors.

Cu 3d electrons exhibit strong correlations.

Excitonic properties were characterized using BSE.

Abstract

Ab initio investigation of the two porous coordination polymers Cu[Cu(pdt)$ _{2} $] and Cu[Ni(pdt)$ _{2} $] has been performed. The dispersion laws and partial density of states was obtained with the PBE0 hybrid functional. The results found here show that the materials under consideration are degenerate $p$-type semiconductors. Here, the effect of partial self-interaction removing of the strongly correlated 3$d$ electrons of Cu and Ni was examined. In case of Cu-containing materials, the obtained results confirm that the 3$d$ electrons of Cu reveal strong correlations, and, therefore, their electronic properties could be evaluated by means of a hybrid functional of the exchange-correlation energy. We also obtained quasiparticle properties within the Green's function (G0W0) and Bethe-Salpeter approaches. The last one was used in order to examine excitonic properties in the degenerate semiconductors. The imaginary part of the dielectric function was obtained within random-phase approximation as well as the Bethe-Salpeter approach.