Ab initio correlation effects on the electronic and transport properties of metal(II)-phthalocyanine-based devices.

Using first-principles calculations in the framework of density functional theory, we investigated the electronic and transport properties of metal(II)-phthalocyanine (M(II)Pc) systems, both in a single-molecule configuration and in a model device geometry. In particular, using copper(II)-Pc and manganese(II)-Pc as prototypical examples, we studied how electronic correlations on the central metal ion influence the analysis of the electronic structure of the system and we demonstrated that the choice of the exchange-correlation functional, also beyond the standard local or gradient corrected level, is of crucial importance for a correct interpretation of the data. Finally, our electronic transport simulations have shown that M(II)Pc-based devices can act selectively as molecular conductors, as in the case of copper, or as spin valves, as in the case of manganese, demonstrating once more the great potential of these systems for molecular nanoelectronics applications.