Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, P.O. Box 9502, 2300 RA, Leiden, The Netherlands.
Phys Chem Chem Phys. 2021 Dec 22;24(1):197-210. doi: 10.1039/d1cp04218a.
Sustainable solutions for hydrogen production, such as dye-sensitized photoelectrochemical cells (DS-PEC), rely on the fundamental properties of its components whose modularity allows for their separate investigation. In this work, we design and execute a high-throughput scheme to tune the ground state oxidation potential (GSOP) of perylene-type dyes by functionalizing them with different ligands. This allows us to identify promising candidates which can then be used to improve the cell's efficiency. First, we investigate the accuracy of different theoretical approaches by benchmarking them against experimentally determined GSOPs. We test different methods to calculate the vertical oxidation potential, including with different levels of self-consistency, Kohn-Sham (KS) orbital energies and total energy differences. We find that there is little difference in the performance of these methods. However, we show that it is crucial to take into account solvent effects as well as the structural relaxation of the dye after oxidation. Other thermodynamic contributions are negligible. Based on this benchmark, we decide on an optimal strategy, balancing computational cost and accuracy, to screen more than 1000 dyes and identify promising candidates which could be used to construct more robust DS-PECs.
用于生产氢气的可持续解决方案，如染料敏化光电化学电池（DS-PEC），依赖于其组件的基本特性，其模块化允许对其进行单独研究。在这项工作中，我们设计并执行了一种高通量方案，通过用不同的配体对苝型染料进行功能化来调整其基态氧化电位（GSOP）。这使我们能够识别出有前途的候选物，然后可以用这些候选物来提高电池的效率。首先，我们通过将不同的理论方法与实验确定的 GSOP 进行基准测试来研究它们的准确性。我们测试了不同的方法来计算垂直氧化电位，包括使用不同自洽性水平的 KS 轨道能量和总能量差。我们发现这些方法的性能差异很小。然而，我们表明，考虑溶剂效应以及氧化后染料的结构弛豫至关重要。其他热力学贡献可以忽略不计。基于这个基准，我们决定采用一种最佳策略，平衡计算成本和准确性，筛选超过 1000 种染料，并确定有前途的候选物，这些候选物可用于构建更稳健的 DS-PEC。
