重新考虑MOBH35金属-有机势垒高度：局域轨道耦合团簇方法在不同静态相关区的性能
The MOBH35 metal-organic barrier heights reconsidered: performance of local-orbital coupled cluster approaches in different static correlation regimes
摘要：
我们重新审视了MOBH 35（金属有机屏障高度，35个反应）基准[铁，M。一、Janes，T. J. Phys. Chem. A 2019，123（17），3761-3781; ibid.2019，123，6379-6380]对于实际的有机金属催化反应，使用典型的CCSD（T）和对其的定域轨道近似。对于低水平的静态相关性，所有的DLPNO-CCSD（T）、PNO-LCCSD（T）和LNO-CCSD（T）都表现良好;对于中等强水平的静态相关，DLPNO-CCSD（T）和（T1）可能灾难性地崩溃，并且PNO-LCCSD（T）也是脆弱的。相比之下，LNO-CCSD（T）在越来越紧的收敛设置下平滑地收敛到规范CCSD（T）答案。我们修正的MOBH 35参考值与原始值有实质性差异的仅有两个反应是反应9和较小程度的反应8，两者都涉及铁。为了评估MOBH 35的DFT方法，最好完全删除反应9，因为其严重的静态相关性要求太高。DLPNO-CCSD（T）和DLPNO-CCSD（T1）之间的差异大小是DLPNO-CCSD（T1）与经典CCSD（T）相比误差的合理预测因素; [...]
英文摘要：
We have revisited the MOBH35 (Metal-Organic Barrier Heights, 35 reactions) benchmark [Iron, M. A.; Janes, T. J. Phys. Chem. A 2019, 123 (17), 3761-3781; ibid. 2019, 123, 6379-6380] for realistic organometallic catalytic reactions, using both canonical CCSD(T) and localized orbital approximations to it. For low levels of static correlation, all of DLPNO-CCSD(T), PNO-LCCSD(T), and LNO-CCSD(T) perform well; for moderately strong levels of static correlation, DLPNO-CCSD(T) and (T1) may break down catastrophically, and PNO-LCCSD(T) is vulnerable as well. In contrast, LNO-CCSD(T) converges smoothly to the canonical CCSD(T) answer with increasingly tight convergence settings. The only two reactions for which our revised MOBH35 reference values differ substantially from the original ones are reaction 9 and to a lesser extent 8, both involving iron. For the purpose of evaluating DFT methods for MOBH35, it would be best to excise reaction 9 entirely as its severe level of static correlation is just too demanding a test. The magnitude of the difference between DLPNO-CCSD(T) and DLPNO-CCSD(T1) is a reasonably good predictor for errors in DLPNO-CCSD(T1) compared to canonical CCSD(T); [...]
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