Quantum chemical investigations aimed at modeling highly efficient zinc porphyrin dye sensitized solar cells.

Zinc tetraphenylporphyrin (ZnTPP) was modified by a push-pull strategy and then density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed for the resulting derivatives. The smallest HOMO-LUMO energy gaps were found in ZnTPP-6 and ZnTPP-7, which had nitro substituents and a conjugated chain, while the largest was observed for ZnTPP-5. The energy gaps of all of the systems designed in this work were smaller than that of ZnTPP. Clear intramolecular charge transfer was observed from donor to acceptor in ZnTPP-6 and ZnTPP-7, which had nitro groups at positions R8, R9, and R10, as well as in ZnTPP-3 and ZnTPP-4, which had cyano groups at those positions. The narrow band gaps (compared to that of ZnTPP) of these designed systems, where the LUMO is above the conduction band of TiO(2) and the HOMO is below the redox couple, indicate that they are efficient sensitizers. The B bands of these newly designed derivatives, except for ZnTPP-5, are redshifted compared with the B band of ZnTPP.