ABSTRACT
The performance of ruthenium dye sensitized solar cells (DSSC) with different types of ligand was studied by means of a theoretical model where the ruthenium complex is bound to two [Ti(OH)3](+) units, instead of the more usual cluster TiO2 model. Electron injection is proposed to proceed from a thermalized (3)MLCT state rather than from higher vibrational excited states. The efficiency of the dye linked to the two [Ti(OH)3](+) units was determined in terms of a global index (ξ), calculated as the product of three theoretical indexes (FI) built from the results of time-dependent density functional theory (TDDFT) calculations. The index considers the harvested and delivered energy (F1), the charge transferred to the semiconductor (F2), and dye regeneration (F3). The results show that this set of parameters is unique for each dye, and allows the comparative evaluation of the performance of a series of dyes, with a different ancillary ligand at each stage of the cell operation. The method provides insights that can help explain the improved performance of N3 and black dyes compared to other dyes.
ABSTRACT
In this work, we report the synthesis and a study on the degree of electronic delocalization in the asymmetric mixed valence complexes [CpFe(C(8)H(6))Fe(C(8)H(7))](+), 3a(+), and [CpCo(C(8)H(6))Fe(C(8)H(7))](+), 3b(+), (Cp = C(5)Me(5), C(8)H(6) = pentalenyde, C(8)H(7) = hydropentalenyde, and = ((3,5(CF(3))(2)C(6)H(3))(4)B(-))). Electrochemical methods, (57)Fe Mössbauer spectroscopy, electronic spectroscopy, and electron paramagnetic resonance were used for this purpose. Although the anti conformation of the complexes precludes any metal-metal interaction, all the techniques employed show that 3a(+) is a electronic delocalized system, while 3b(+) behaves as two individual metallic centers with localized electron density.
