Zooming in on the O–O Bond Formation—An Ab Initio Molecular Dynamics Study Applying Enhanced Sampling Techniques,Journal of Chemical Theory and Computation

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Zooming in on the O–O Bond Formation—An Ab Initio Molecular Dynamics Study Applying Enhanced Sampling Techniques
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2020-03-24 , DOI: 10.1021/acs.jctc.9b01207
Mauro Schilling ₁ , Richard A. Cunha ₁ , Sandra Luber ₁

Affiliation

Mastering artificial water oxidation is a key step on moving away from fossil fuels toward a carbon emission-free society. Unfortunately, the crucial chemical transformation of this reaction, the O–O bond formation, is still not well understood, even though there are various known active water oxidation catalysts, such as Ru-based catalysts bearing a Py5 ligand. Those were recently investigated both experimentally and using a static density functional theory (DFT) approach based on geometry optimizations. In this work, we shed light on the O–O formation catalyzed by those Ru-based complexes, utilizing enhanced sampling techniques such as the Bluemoon ensemble and metadynamics together with high-performance DFT-based molecular dynamics simulations. This allowed unprecedented detailed insights into the process of the oxygen–oxygen bond formation and also extended the view on the reaction network and the flexibility of the product state because of the consideration of the dynamics at ambient conditions. Our model system contained both the catalyst and a large number of explicit water molecules which can participate in the reaction and stabilize intermediates. Moreover, it is demonstrated how crucial the choice of the collective variable is in order to capture relevant features of the studied reaction.

中文翻译：

放大O–O键的形成-应用增强采样技术的从头算分子动力学研究

掌握人工水氧化是从化石燃料迈向无碳排放社会的关键一步。不幸的是，即使存在各种已知的活性水氧化催化剂，例如带有Py5配体的Ru基催化剂，该反应的关键化学转化（O-O键的形成）仍未得到很好的理解。最近对它们进行了实验研究，并使用了基于几何优化的静态密度泛函理论（DFT）方法。在这项工作中，我们利用增强的采样技术（如Bluemoon集成和元动力学以及基于DFT的高性能分子动力学模拟），揭示了那些基于Ru的配合物催化的O–O形成。由于考虑到环境条件下的动力学特性，这使人们对氧-氧键形成过程有了空前的详细见解，并且扩展了反应网络和产物状态灵活性的观点。我们的模型系统既包含催化剂，又包含大量显性水分子，它们可以参与反应并稳定中间体。此外，证明了集体变量的选择对于捕获所研究反应的相关特征至关重要。我们的模型系统既包含催化剂，又包含大量显性水分子，它们可以参与反应并稳定中间体。此外，证明了集体变量的选择对于捕获所研究反应的相关特征至关重要。我们的模型系统既包含催化剂，又包含大量显性水分子，它们可以参与反应并稳定中间体。此外，证明了集体变量的选择对于捕获所研究反应的相关特征至关重要。

更新日期：2020-04-24

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