The MOBH35 Metal-Organic Barrier Heights Reconsidered: Performance of Local-Orbital Coupled Cluster Approaches in Different Static Correlation Regimes.
The MOBH35 Metal-Organic Barrier Heights Reconsidered: Performance of Local-Orbital Coupled Cluster Approaches in Different Static Correlation Regimes.
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DOI：
10.1021/acs.jctc.1c01126
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发表时间：
2022-02-08
影响因子：
5.5
通讯作者：
Martin JML
中科院分区：
文献类型：
--
作者：
Semidalas E;Martin JML
我们重新审视了MOBH 35（金属-有机势垒高度，35个反应）基准[，（（），），−;同上，，-]，用于实际的有机金属催化反应，使用规范CCSD（T）及其定域轨道近似。对于低水平的静态相关性，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的密度泛函理论（DFT）方法，最好完全去除反应9，因为其严重的静态相关性使其对测试要求太高。与标准CCSD（T）相比，DLPNO-CCSD（T）和DLPNO-CCSD（T1）之间的差异幅度是DLPNO-CCSD（T1）中错误的合理良好预测因子;否则，监测所有T1、D1、max| Tia|和1/（εLUMO - εHOMO）应该为潜在的问题提供足够的警告。我们的结论并不特定于def 2-SVP基组，但对于较大的def 2-TZVPP在很大程度上是保守的，因为它们对于较小的def 2-SV（P）：后者可能是针对规范CCSD（T）进行校准的经济选择。最后，静态相关性的诊断统计聚类成组对应于（1）波函数中的单激发的重要性;（2a）小的带隙，弱分离（2b）相关熵;和（3）热化学相关能量的重要性，以及DFT反应能量相对于HF交换百分比的斜率。最后，变量减少分析表明，T1、IND/Itot和基于交换的诊断A100[TPSS]提供了关于多引用字符的许多信息。
We have revisited the MOBH35 (Metal–Organic Barrier Heights, 35 reactions) benchmark [, , , ( (), ), −; ibid. , , –] 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 density functional theory (DFT) methods for MOBH35, it would be best to remove reaction 9 entirely as its severe level of static correlation makes it just too demanding for 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); otherwise, monitoring all of T1, D1, max|tiA|, and 1/(εLUMO – εHOMO) should provide adequate warning for potential problems. Our conclusions are not specific to the def2-SVP basis set but are largely conserved for the larger def2-TZVPP, as they are for the smaller def2-SV(P): the latter may be an economical choice for calibrating against canonical CCSD(T). Finally, diagnostics for static correlation are statistically clustered into groups corresponding to (1) importance of single excitations in the wavefunction; (2a) the small band gap, weakly separated from (2b) correlation entropy; and (3) thermochemical importance of correlation energy, as well as the slope of the DFT reaction energy with respect to the percentage of HF exchange. Finally, a variable reduction analysis reveals that much information on the multireference character is provided by T1, IND/Itot, and the exchange-based diagnostic A100[TPSS].
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