Intramolecular Path Determination of Active Electrons on Push‐Pull Oligocarbazole Dyes‐Sensitized Solar Cells
Abstract Several push‐pull oligocarbazole dye‐sensitizers have been studied using theoretical methods in order to better understand the relationship between structural electronic or optical properties and intramolecular path of active electrons during the ionization and injection processes. DFT/TD‐D...
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Wiley-VCH
2019-05-01
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| Series: | ChemistryOpen |
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| Online Access: | https://doi.org/10.1002/open.201800224 |
| _version_ | 1818487454231953408 |
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| author | Salma Trabelsi Nouha Kouki Mahamadou Seydou François Maurel Bahoueddine Tangour |
| author_facet | Salma Trabelsi Nouha Kouki Mahamadou Seydou François Maurel Bahoueddine Tangour |
| author_sort | Salma Trabelsi |
| collection | DOAJ |
| description | Abstract Several push‐pull oligocarbazole dye‐sensitizers have been studied using theoretical methods in order to better understand the relationship between structural electronic or optical properties and intramolecular path of active electrons during the ionization and injection processes. DFT/TD‐DFT calculations were performed on a series of five dye sensitizers. They differ by the presence of electron donating group (EDG) by inductive effect (noted+I) or electron releasing group (ERG) by mesomeric effect (noted+M) or electron withdrawing group by inductive effect (noted‐I) on the pushed part of the dyes studied. Our work focused on the internal distribution of electrons in the different parts of dye that are the push/pull moieties and the π‐bridge. The study concerned the ground state, the electronic transition process and the excited state. In each situation, the fragment acting in the ionization or transition phenomena were identified. In the ground state, the electrons of the push part appear to be the least bound because they have the highest probabilities of ionization. In the excited state, the ionized atoms are essentially positioned in the pushing part and some neighboring atoms of the bridge. In the electronic transition, the active atoms are located in the π‐conjugated part but only on the side adjacent to the acceptor group. To arrive to this conclusion, we optimized the structures of the five dyes in their ground and excited states. We calculated the atomic charges, the wavelengths and intensities of electronic transitions in the visible domain, the reorganization energies as well as the oxidation potential. It appears that +M donor ligands improve the performance of a dye because the great distribution of atoms to be ionized in the push parts. |
| first_indexed | 2024-12-10T16:37:51Z |
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| institution | Directory Open Access Journal |
| issn | 2191-1363 |
| language | English |
| last_indexed | 2024-12-10T16:37:51Z |
| publishDate | 2019-05-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryOpen |
| spelling | doaj.art-654c9e5bdf824a5394e48ce00aafd5242022-12-22T01:41:20ZengWiley-VCHChemistryOpen2191-13632019-05-018558058810.1002/open.201800224Intramolecular Path Determination of Active Electrons on Push‐Pull Oligocarbazole Dyes‐Sensitized Solar CellsSalma Trabelsi0Nouha Kouki1Mahamadou Seydou2François Maurel3Bahoueddine Tangour4University of Tunis El Manar Research Unity of Modeling in Fundamental Sciences and Didactics, IPEIEM, BP 254 El Manar 2 2096 Tunis TunisiaUniversity of Tunis El Manar Research Unity of Modeling in Fundamental Sciences and Didactics, IPEIEM, BP 254 El Manar 2 2096 Tunis TunisiaUniversity Paris Diderot Sorbonne Paris Cite, ITODYS. UMR 7086 CNRS 15 rue J. A. de Baïf 75205 Paris Cedex 13 France.University Paris Diderot Sorbonne Paris Cite, ITODYS. UMR 7086 CNRS 15 rue J. A. de Baïf 75205 Paris Cedex 13 France.University of Tunis El Manar Research Unity of Modeling in Fundamental Sciences and Didactics, IPEIEM, BP 254 El Manar 2 2096 Tunis TunisiaAbstract Several push‐pull oligocarbazole dye‐sensitizers have been studied using theoretical methods in order to better understand the relationship between structural electronic or optical properties and intramolecular path of active electrons during the ionization and injection processes. DFT/TD‐DFT calculations were performed on a series of five dye sensitizers. They differ by the presence of electron donating group (EDG) by inductive effect (noted+I) or electron releasing group (ERG) by mesomeric effect (noted+M) or electron withdrawing group by inductive effect (noted‐I) on the pushed part of the dyes studied. Our work focused on the internal distribution of electrons in the different parts of dye that are the push/pull moieties and the π‐bridge. The study concerned the ground state, the electronic transition process and the excited state. In each situation, the fragment acting in the ionization or transition phenomena were identified. In the ground state, the electrons of the push part appear to be the least bound because they have the highest probabilities of ionization. In the excited state, the ionized atoms are essentially positioned in the pushing part and some neighboring atoms of the bridge. In the electronic transition, the active atoms are located in the π‐conjugated part but only on the side adjacent to the acceptor group. To arrive to this conclusion, we optimized the structures of the five dyes in their ground and excited states. We calculated the atomic charges, the wavelengths and intensities of electronic transitions in the visible domain, the reorganization energies as well as the oxidation potential. It appears that +M donor ligands improve the performance of a dye because the great distribution of atoms to be ionized in the push parts.https://doi.org/10.1002/open.201800224push-pull effectsdensity functional theoryreorganization energyatomic ionizationdye sensitizers |
| spellingShingle | Salma Trabelsi Nouha Kouki Mahamadou Seydou François Maurel Bahoueddine Tangour Intramolecular Path Determination of Active Electrons on Push‐Pull Oligocarbazole Dyes‐Sensitized Solar Cells ChemistryOpen push-pull effects density functional theory reorganization energy atomic ionization dye sensitizers |
| title | Intramolecular Path Determination of Active Electrons on Push‐Pull Oligocarbazole Dyes‐Sensitized Solar Cells |
| title_full | Intramolecular Path Determination of Active Electrons on Push‐Pull Oligocarbazole Dyes‐Sensitized Solar Cells |
| title_fullStr | Intramolecular Path Determination of Active Electrons on Push‐Pull Oligocarbazole Dyes‐Sensitized Solar Cells |
| title_full_unstemmed | Intramolecular Path Determination of Active Electrons on Push‐Pull Oligocarbazole Dyes‐Sensitized Solar Cells |
| title_short | Intramolecular Path Determination of Active Electrons on Push‐Pull Oligocarbazole Dyes‐Sensitized Solar Cells |
| title_sort | intramolecular path determination of active electrons on push pull oligocarbazole dyes sensitized solar cells |
| topic | push-pull effects density functional theory reorganization energy atomic ionization dye sensitizers |
| url | https://doi.org/10.1002/open.201800224 |
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