Abstract
The prediction of ground-state redox potentials by quantum chemical methods has a prominent role in the rational design of novel organic photosensitizers both for dye-sensitized solar cells (DSSCs) and photocatalytic systems for the production of H2. Indeed, the ground-state redox potential of the photosensitizers is one of the key parameters to identify the most promising candidates for such applications. Here, the ground-state redox potentials of 16 organic donor-π-acceptor D-π-A and donor-acceptor-π-acceptor D-A-π-A dyes having a medium to large size of the conjugated scaffold are evaluated, using the methods of the Density Functional Theory (DFT), in terms of free energy differences between their neutral and oxidized ground-state forms. These results are compared to the available experimental data and to the computed highest occupied molecular orbital energy −ε(HOMO) values as an approximation of ground-state redox potentials according to Koopmans’ theorem. Using the MPW1K functional in combination with the 6-31+G* basis set, the strategy based on the free energy cycle, including solvent effects, reproduces with a good level of accuracy the observed values (mean absolute error (MAE) < 0.2 eV) and trend of redox potentials within related families of dyes. On the other hand, the −ε(HOMO) values are only able to capture the experimental trends in redox potential values.
Highlights
IntroductionMore recently, as sensitizers in photocatalytic systems for the production of H2 [4,5,6,7]
Organic dyes having a donor-π-acceptor (D-π-A) or donor-acceptor-π-acceptor (D-A-π-A)architecture have been extensively used as photosensitizers in dye-sensitized solar cells (DSSCs) [1,2,3]and, more recently, as sensitizers in photocatalytic systems for the production of H2 [4,5,6,7]
The ground-state redox potential was computed at the MPW1K/6-31+G* level of theory as free energy differences between the neutral and oxidized state of these the procedure described by Pastore et al [15]
Summary
More recently, as sensitizers in photocatalytic systems for the production of H2 [4,5,6,7] In both devices, visible-light absorbing dyes are employed to enhance light harvesting of semiconductor nanoparticles of TiO2. Donor–acceptor D-π-A architectures, have been found able to establish an efficient charge separation: due to the wide diversity of suitable D, A and π fragments a huge number of different sensitizers can be accessed, allowing a fine-tuning of their chemical, optical, energetic, and stability properties. Due to the wide diversity of suitable D, A and π fragments a huge number of different the additional electron acceptor unit can enhanceofthe electronic push−pull effect, sensitizers can be accessed, allowing a fine-tuning their intramolecular chemical, optical, energetic, and stability properties
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