RUI: SusChEM: Towards accurate computational dynamical and mechanistic studies of transition metal homogeneous (photo)catalysis

在这项由化学催化计划和化学系化学理论、模型和计算方法计划资助的项目中，蒙特克莱尔州立大学的亨德里克·埃斯皮斯教授正在应用并开发计算方法来研究使用金属络合物的化学反应的催化作用，并了解分子结构与其作为催化剂的活性之间的关系。一种名为随机相近似方法的计算方法正在开发和改进，以描述催化剂如何激活化学键的基本方面。这种方法也被应用于研究光如何驱动某些催化剂执行特定的反应，也称为光催化。该项目正在为包括催化在内的广泛化学研究提供可用的计算方法工具箱。最终，它可能会推动更高效、更绿色催化剂的开发，这是一个社会和行业都感兴趣的目标。本科生和研究生都参与了这项研究，埃斯皮斯教授参与了蒙特克莱尔州立大学化学课程中计算化学部分的强化。EShuis正在应用和开发计算方法来研究过渡金属均相(光)催化，并主要致力于开发随机相近似方法来描述键活化反应的动力学和机理方面。随机相近似方法的质量正在与实验结果进行基准比较，并与其他从头计算和密度泛函理论方法进行比较。该方法正被用于研究含镍催化剂的碳-碳键活化反应机理，重点是配体组成与反应活性之间的联系，以及光催化三氟甲基化反应机理的研究。随机相近似方法正在进一步发展，用于碳-氢键活化机理的从头算分子动力学研究，并扩展到开壳体系。

In this project funded by the Chemical Catalysis Program and the Chemical Theory, Models and Computational Methods Program of the Division of Chemistry, Professor Hendrik Eshuis of Montclair State University is applying and developing computational methods to study the catalysis of chemical reactions using metal complexes and to understand the relationship between the structure of molecules and their activity as catalysts. A computational method, called the Random Phase Approximation Method, is being developed and refined to described fundamental aspects of how chemical bonds are activated by catalysts. This method is also being applied to study how light can drive certain catalysts to perform specific reactions, also known as photocatalysis. This project is contributing to the toolbox of computational methods available for the study of a wide range of chemistries, including catalysis. Ultimately, it may advance the development of more efficient and greener catalysts, a goal of interest to both society and industry. Both undergraduate and graduate students are involved in this research, and Prof. Eshuis is involved in strengthening the computational chemistry component of the chemistry curriculum at Montclair State University.Prof. Eshuis is applying and developing computational methods to study transition metal homogeneous (photo)catalysis and is primarily focused on the development of the random phase approximation method to describe dynamic and mechanistic aspects of bond activation reactions. The quality of the random phase approximation method is being benchmarked against experimental results and compared to other ab initio and density functional theory methods. The method is being applied to the study of mechanisms of carbon-carbon bond activation reactions by nickel containing catalysts, with a focus on the link between ligand composition and reactivity, as well as in the study of the mechanism of photocatalyzed trifluoromethylation reactions. The random phase approximation method is being further developed to be used in ab initio molecular dynamical studies of mechanisms involving carbon-hydrogen bond activation and extended to open-shell systems.