Estudo sobre a estrutura eletrônica de ftalocianinas metaladas para aplicação em células solares sensibilizadas por corante

Abstract

The electronic properties of push-pull substituted, zinc(II) (ZnPc), aluminum(III) (AlPc), and ruthenium(II) (RuPc), metal-phthalocyanine derivatives, presenting two electron donating groups (diethylamine) and two electron withdrawing groups (carboxylic) was studied using the Density Functional Theory (DFT) with B3LYP exchange-correlation functional in the vacuum and under the presence of solvent (DMSO), aiming their application in dye-sensitized solar cells (DSSC). For the excited states, the time-dependent approach of DFT (TD-DFT) was applied. In the transition for the excited state it was evidenced a charge transfer from donor to acceptor groups which results in large electronic rearrangement inducing the bathochromism when adding DMSO (a polar solvent). This electronic transfer is directed to the acceptor groups (benzoic groups), mainly in RuPc molecule, which enables bigger probability in the electronic injection into the semiconductor s conduction band. HOMO s energy to the ZnPc and AlPc are sufficiently below the redox potential of the electrolyte and LUMO s energy, in all compounds, is above the conduction band of the oxide. Those push-pull molecules present panchromism, important for the application of these compounds in DSSC since they can absorb photons in a large range of energies. NBO analysis suggests that the ruthenium presents strong coordination with the nitrogen atoms of the macrocycle, which allows a larger participation of this metal in the electronic transition. The ionization energy and electron affinity were calculated aiming to quantify the energetic barrier in the electron gain / loss.