Daoudi Syrine, Semmeq Abderrahmane, Badawi Michael, Assfeld Xavier, Arfaoui Youssef, Pastore Mariachiara
CNRS & Université de Lorraine, Laboratoire de Physique et Chimie Théoriques, Boulevard des Aiguillettes, BP, 70239 54506, Vandoeuvre-lès-Nancy Cedex, France.
Laboratory of Physical Chemistry of Condensed Materials, Faculty of Mathematical, Physical and Natural Sciences of Tunis, University of Tunis El Manar, Campus Farhat-Hached, 1068, Tunis, Tunisia.
J Comput Chem. 2019 Nov 5;40(29):2530-2538. doi: 10.1002/jcc.26027. Epub 2019 Jul 11.
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 E excitation energies and the energy levels alignment (red-ox properties) at the interface with the TiO . We find that both vertical and E excitation energies are accurately reproduced by range-separated functionals, among which the ωB97X-D delivers the lowest absolute deviations from experiments. When the dye/TiO 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 ωB97X-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. © 2019 Wiley Periodicals, Inc.
研究了用于染料敏化光合成电池的七种游离碱卟啉，目的是评估不同密度泛函理论（DFT）和含时DFT方法在再现其结构、垂直激发能和E激发能以及与TiO界面处的能级排列（氧化还原性质）方面的能力。我们发现，范围分离泛函能准确再现垂直激发能和E激发能，其中ωB97X-D与实验的绝对偏差最小。当对染料/TiO界面进行建模时，只有使用B3LYP泛函才能获得物理界面能量学；另一方面，M06-2X（54%的交换率）以及测试的两种长程校正方法（CAM-B3LYP和ωB97X-D）相对于染料的最低未占据分子轨道（LUMO）过度降低了半导体导带能级的稳定性，预测不存在电子注入途径。© 2019威利期刊公司。
