The MOBH35 Metal-Organic Barrier Heights Reconsidered: Performance of Local-Orbital Coupled Cluster Approaches in Different Static Correlation Regimes.

Abstract

We have revisited the MOBH35 (Metal–Organic Barrier Heights, 35 reactions) benchmark [Iron, Janes, J. Phys. Chem. A, 2019, 123 ( (17), ), 3761−378130973722; 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 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].