Amanollahi Zohreh, Lampe Lukas, Bensberg Moritz, Neugebauer Johannes, Feldt Milica
Leibniz Institute for Catalysis (LIKAT), Albert-Einstein-Str. 29A, 18059 Rostock, Germany.
Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 36, 48149 Münster, Germany.
Phys Chem Chem Phys. 2023 Feb 8;25(6):4635-4648. doi: 10.1039/d2cp05056k.
In this work, we investigate the accuracy of the local molecular orbital molecular orbital (LMOMO) scheme and projection-based wave function-in-density functional theory (WF-in-DFT) embedding for the prediction of reaction energies and barriers of typical reactions involving transition metals. To analyze the dependence of the accuracy on the system partitioning, we apply a manual orbital selection for LMOMO as well as the so-called direct orbital selection (DOS) for both approaches. We benchmark these methods on 30 closed shell reactions involving 16 different transition metals. This allows us to devise guidelines for the manual selection as well as settings for the DOS that provide accurate results within an error of 2 kcal mol compared to local coupled cluster. To reach this accuracy, on average 55% of the occupied orbitals have to be correlated with coupled cluster for the current test set. Furthermore, we find that LMOMO gives more reliable relative energies for small embedded regions than WF-in-DFT embedding.
在这项工作中，我们研究了局域分子轨道（LMOMO）方案以及基于投影的波函数嵌入密度泛函理论（WF-in-DFT）在预测涉及过渡金属的典型反应的反应能量和势垒方面的准确性。为了分析准确性对体系划分的依赖性，我们对LMOMO应用了手动轨道选择，并且对这两种方法都应用了所谓的直接轨道选择（DOS）。我们在涉及16种不同过渡金属的30个闭壳层反应上对这些方法进行了基准测试。这使我们能够制定手动选择的指导方针以及DOS的设置，与局域耦合簇方法相比，这些设置能在2千卡/摩尔的误差范围内提供准确结果。为了达到这种准确性，对于当前测试集，平均55%的占据轨道必须与耦合簇相关联。此外，我们发现对于小的嵌入区域，LMOMO给出的相对能量比WF-in-DFT嵌入更可靠。
