The dynamics of light-induced interfacial charge transfer of different dyes in dye-sensitized solar cells studied by <i>ab initio</i> molecular dynamics
Lanlan He, Yu Guo, Lars Kloo
Abstract
to the dye. It is notable that the electronic coupling/transfer rates differ significantly between the snapshot configurations harvested from the aiMD simulations. The differences are significant and indicate that a single geometrically optimized conformation normally obtained from static quantum-chemistry calculations may provide arbitrary results. Both protonated and deprotonated dye systems were studied. The differences mainly appear in the rate constant of recombination loss between the protonated and the deprotonated dyes, where recombination losses take place at significantly higher rates. The inclusion of lithium ions close to the deprotonated dye carboxylate anchoring group mitigates recombination in a similar way as when protons are retained at the carboxylate group. This may give insight into the performance-enchancing effects of added salts of polarizing cations to the DSSC electrolyte. In addition, solvent effects can retard charge recombination by about two orders of magnitude, which demonstrates that the presence of a solvent will increase the lifetime of injected electrons and thus contribute to a higher PCE of DSSCs. It is also notable that no simple correlation can be identified between high/low transfer rate constants and specific structural arrangements in terms of atom-atom distances, angles or dihedral arrangements of dye sub-units.