http://www.cnr.it/ontology/cnr/individuo/prodotto/ID195369
Computational Spectroscopy Characterization of the Species Involved in Dye Oxidation and Regeneration Processes in Dye-Sensitized Solar Cells (Articolo in rivista)
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- Computational Spectroscopy Characterization of the Species Involved in Dye Oxidation and Regeneration Processes in Dye-Sensitized Solar Cells (Articolo in rivista) (literal)
- Anno
- 2011-01-01T00:00:00+01:00 (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
- 10.1021/jp2049475 (literal)
- Alternative label
Maria Grazia Lobello, Simona Fantacci, Filippo De Angelis (2011)
Computational Spectroscopy Characterization of the Species Involved in Dye Oxidation and Regeneration Processes in Dye-Sensitized Solar Cells
in Journal of physical chemistry. C
(literal)
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- Maria Grazia Lobello, Simona Fantacci, Filippo De Angelis (literal)
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- http://pubs.acs.org/doi/abs/10.1021/jp2049475 (literal)
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- Istituto CNR di Scienze e Tecnologie Molecolari (ISTM-CNR), c/o Dipartimento di Chimica, Università di Perugia, Via elce di Sotto 8, I-06213, Perugia, Italy (literal)
- Titolo
- Computational Spectroscopy Characterization of the Species Involved in Dye Oxidation and Regeneration Processes in Dye-Sensitized Solar Cells (literal)
- Abstract
- We investigate the spectroscopic signature of oxidized dyes and of their complexes with I- occurring in the oxidation/regeneration process in dye-sensitized solar cells. Following the transient absorption spectroscopy study by Clifford et al. [J. Phys. Chem. C, 2007, 111, 6561-6567], we report a DFT/TDDFT study on the geometrical, electronic, and optical properties of the neutral and cationic [RuII(dcbpy)2(X)2] complexes, where dcbpy = 4,4?-dicarboxy-2,2?-bipyridyl and X = NCS and CN, and of their adducts with I-. We focus on the interaction between the oxidized dyes and iodide and perform DFT/TDDFT calculations using a continuum model of solvation on the complexes of interest, thus providing a picture of the electronic structure of the oxidized dyes and their adducts with I-. We find a good agreement between the simulated and the experimental absorption spectra, including the absorption band in the IR region that is experimentally assigned to the [dye+:I-] complexes. In line with Clifford et al., we find such band in the IR to overlap substantially with that of the dye cation for X = NCS, whereas it is readily identified for X = CN, for which the LMCT band of the cation has negligible intensity. Our results confirm the assignment of the IR band to a charge-transfer transition occurring within the [dye+:I-] complex, corresponding to shift of electron density from the Ru-X HOMOs to the LUMO based on the I atom. We expect our study to provide the required theoretical basis for interpretation of further transient spectroscopic data of interest in the DSCs field. (literal)
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