Journal
JOURNAL OF COMPUTATIONAL CHEMISTRY
Volume 40, Issue 29, Pages 2530-2538Publisher
WILEY
DOI: 10.1002/jcc.26027
Keywords
DFT; TDDFT; free base porphrins; dye sensitized TiO2; water splitting
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Funding
- ANR JCJC HELIOSH2 [ANR-17-CE05-0007-01]
- HPC resources from GENCI-CCRT/CINES [2018-A0010810139]
- Agence Nationale de la Recherche (ANR) [ANR-17-CE05-0007] Funding Source: Agence Nationale de la Recherche (ANR)
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Seven free base porphyrins employed in dye-sensitized photoelectrosynthetic cells are investigated with the aim of benchmarking the ability of different density functional theory (DFT) and time-dependent DFT approaches in reproducing their structure, vertical, and E0-0 excitation energies and the energy levels alignment (red-ox properties) at the interface with the TiO2. We find that both vertical and E0-0 excitation energies are accurately reproduced by range-separated functionals, among which the omega B97X-D delivers the lowest absolute deviations from experiments. When the dye/TiO2 interface is modeled, the physical interfacial energetics is only obtained when the B3LYP functional is employed; on the other hand, M06-2X (54% of exchange) and the two long-range corrected approaches tested (CAM-B3LYP and omega B97X-D) excessively destabilize the semiconductor conduction band levels with respect to the dye's lowest unoccupied molecular orbitals (LUMOs), predicting no pathway for electron injection. (c) 2019 Wiley Periodicals, Inc.
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