Accurate Description of Catalytic Selectivity: Challenges and Opportunities for the Development of Density Functional Approximations
Accurate Description of Catalytic Selectivity: Challenges and Opportunities for the Development of Density Functional Approximations
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DOI：
10.31635/ccschem.020.202000635
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发表时间：
2021-01-01
期刊：
影响因子：
11.2
通讯作者：
Zhang, Igor Ying
中科院分区：
文献类型：
--
作者：
Chen, Zhe-Ning;Shen, Tonghao;Zhang, Igor Ying
准确描述催化选择性对理论模拟提出了巨大的挑战。由于缺乏一个定义明确的催化选择性的基准集，即使是广泛使用的密度泛函近似（DFAs）的性能还有待验证。本工作报告了一个测试集的基础上选择性氢化的α，β-不饱和醛钌（Ru）氢化物配合物催化。特别注意的是基准的区域选择性醛不饱和醇或饱和醛。精确的参考数据计算的耦合集群单，双，微扰三重激发[CCSD（T）]的方法，完全基于设定的限制大规模并行实施。此外，我们进行了微观动力学模拟的基础上，CCSD（T）的能量分布，服务于最直接的标准的性能的DFAs对加氢反应的催化选择性。使用这个测试集，我们发现了内在的困难，半局部和混合泛函这样一个目的。在XYG 3型双杂交（xDH）框架的背景下，我们表明，只有当多体非动态相关效应被充分考虑时，这种特殊的挑战才能通过最高层泛函来解决。最近提出的xDH，即scsRPA，显示出前所未有的准确性，平均误差仅为5%。通过scsRPA预测的动力学选择性与参考值非常一致，揭示了顶级DFA对于氢化反应的催化选择性的可靠描述的独特多功能性。[图形]。
An accurate description of catalytic selectivity poses an enormous challenge for theoretical simulations. Due to the absence of a well-defined benchmark set on the catalytic selectivity, the performance of even the widely used density functional approximations (DFAs) is yet to be validated. This work reports a test set based on the selective hydrogenation of alpha,beta-unsaturated aldehydes catalyzed by ruthenium (Ru) hydride complexes. Special attention is paid to benchmark the regioselectivity of aldehydes to either unsaturated alcohols or saturated aldehydes. Accurate reference data were calculated by the massive parallel implementation of the coupled-cluster single, double, and perturbative triple excitations [CCSD(T)] approach, based completely on set limits. Furthermore, we performed the microkinetic simulation based on the CCSD(T) energy profiles, serving the most direct criteria for the performance of DFAs on catalytic selectivity of hydrogenation reactions. Using this test set, we uncovered the intrinsic difficulty of semilocal and hybrid functionals for such a purpose. In the context of the XYG3-type double hybrid (xDH) framework, we showed that this particular challenge could be addressed by the top rung functionals only when the many-body nondynamic correlation effect was accounted for adequately. A recently proposed xDH, namely scsRPA, showed unprecedented accuracy with only 5% error on average. The predicted kinetic selectivity by scsRPA is in close agreement with the reference value, revealing a unique versatility of the top rung DFAs for a reliable description of catalytic selectivity of hydrogenation reactions.[GRAPHICS].