The role of lithium cations on the photochemistry of ruthenium complexes in dye-sensitized solar cells: A TDDFT study with the BCL model

[Display omitted] •Theoretical calculations predict that a Ruhtenium Dye-Lithium adduct could be photo chemically generated.•Experimental trends are well reproduce by TDDFT calculation.•The BCL model predict an enhancement of the photo conversion efficiency when Lithium is present. Lithium cations have been shown to impart an electrostatic Stark effect on molecules bound to mesoporous metal oxides commonly used in dye-sensitized solar cells. Herein, using the Barrera-Crivelli-Loeb theoretical model accompanied by Time Dependent Density Functional Theory calculations, we examined the influence that lithium cations have on the performance of dye-sensitized solar cells that incorporate [Ru(dmb)2(dcbH)]2+ sensitizers, where dmb is 4,4′-dimethyl-2,2′-bipyridine and dcbH is 4,4′-dicarboxylic acid-2,2′-bipyridine was examined. Simulations suggest that an enhanced photocurrent occurs in the presence of lithium cations, which is attributed to the photochemical generation of an excited-state dye–lithium adduct. In this adduct, a lithium cation is interacting with the carbonyl moieties of the dcbH ligands, which results in a bathochromic shift of the [Ru(dmb)2(dcbH)]2+ metal-to-ligand charge-transfer spectral band. This shift in absorption can be canceled by introducing a hypothetical dipolar electric field of 7.3 MV/cm, in good agreement with experimentally reported values for Stark effects observed under solar excitation of TiO2 functionalized with these types of sensitizer molecules. This indicates that lithium cations not only interact with the metal-oxide semiconductor, as shown previously, but also interact directly with the dye upon photoexcitation, something that should be considered when designing and evaluating new sensitizers.