Electron transport properties of PAl12-based cluster complexes

The electronic transport properties of PAl12-based cluster complexes are investigated by density functional theory (DFT) in combination with the non-equilibrium Green's function (NEGF) method. Joining two PAl12 clusters via a germanium linker creates a stable semiconducting complex with a large HOMO-LUMO gap. Sequential attachment of an electron-donating ligand, N-ethyl-2-pyrrolidone, to one of the two linked clusters results in the shifting of the electronic spectrum of the ligated cluster while the energy levels of the unligated cluster are mostly unchanged. Using this approach, one can eventually align the HOMO of the ligated cluster to the LUMO of the non-ligated cluster, thereby significantly reducing the HOMO-LUMO gap of the complex. As a result, the transport properties of the complex are highly dependent on the number of attached ligands. Although a single ligand is observed to generally decrease the current, the inclusion of two or more ligands shows a significant increase in the amount of current at most voltages. The resulting increase of the current can be attributed to two factors, first the reduction in the HOMO-LUMO gap due to ligand attachment which has moved the transmission orbitals into the bias window. Secondly, when two or more ligands are attached to the complex, the HOMOs become delocalized across the scattering region, and this significantly enhances the currents.