Ground-State Redox Potentials Calculations of D-?-A and D-A-?-A Organic Dyes for DSSC and Visible-Light-Driven Hydrogen Production

Sanaz Mohammadpourasl, Fabrizia Fabrizi de Biani, Carmen Coppola, Maria Laura Parisi, Lorenzo Zani, Alessio Dessì, Massimo Calamante, Gianna Reginato, Riccardo Basosi and Adalgisa Sinicropi
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Sanaz Mohammadpourasl: R 2 ES Lab, Department of Biotechnology, Chemistry and Pharmacy, University of Siena, 53100 Siena, Italy
Fabrizia Fabrizi de Biani: Department of Biotechnology, Chemistry and Pharmacy, University of Siena, 53100 Siena, Italy
Carmen Coppola: R 2 ES Lab, Department of Biotechnology, Chemistry and Pharmacy, University of Siena, 53100 Siena, Italy
Maria Laura Parisi: R 2 ES Lab, Department of Biotechnology, Chemistry and Pharmacy, University of Siena, 53100 Siena, Italy
Lorenzo Zani: National Research Council, Institute for the Chemistry of OrganoMetallic Compounds (CNR-ICCOM), 50019 Sesto Fiorentino, Italy
Alessio Dessì: National Research Council, Institute for the Chemistry of OrganoMetallic Compounds (CNR-ICCOM), 50019 Sesto Fiorentino, Italy
Massimo Calamante: National Research Council, Institute for the Chemistry of OrganoMetallic Compounds (CNR-ICCOM), 50019 Sesto Fiorentino, Italy
Gianna Reginato: National Research Council, Institute for the Chemistry of OrganoMetallic Compounds (CNR-ICCOM), 50019 Sesto Fiorentino, Italy
Riccardo Basosi: R 2 ES Lab, Department of Biotechnology, Chemistry and Pharmacy, University of Siena, 53100 Siena, Italy
Adalgisa Sinicropi: R 2 ES Lab, Department of Biotechnology, Chemistry and Pharmacy, University of Siena, 53100 Siena, Italy

Energies, 2020, vol. 13, issue 8, 1-10

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 H 2 . 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.

Keywords: dye-sensitized solar cells; first principle modelling; ground-state oxidation potentials; solar energy devices; solar fuel devices; organic sensitizers; photocatalytic hydrogen production (search for similar items in EconPapers)
JEL-codes: Q Q0 Q4 Q40 Q41 Q42 Q43 Q47 Q48 Q49 (search for similar items in EconPapers)
Date: 2020
References: View references in EconPapers View complete reference list from CitEc
Citations: View citations in EconPapers (1)

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