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, 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); [...]

J. Chem. Theor. Comput. 18, ASAP (2022). CC:BY 4.0. Dedicated to the memory of Shimon Vega (1943-2021)

References in corpus (12)

• W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions
• W3 theory: robust computational thermochemistry in the kJ/mol accuracy range
• Comment on: "Estimating the Hartree-Fock limit from finite basis set calculations" [Jensen F (2005) Theor Chem Acc 113:267]
• Basis set convergence of post-CCSD contributions to molecular atomization energies
• Separation of Dynamic and Nondynamic Correlation
• Local descriptors of dynamic and nondynamic correlation
• Exploring Avenues Beyond Revised DSD Functionals: I. range separation, with xDSD as a special case
• Performance of Localized Coupled Cluster Methods in a Moderately Strong Correlation Regime: Hückel-Möbius Interconversions in Expanded Porphyrins
• Canonical and DLPNO-based G4(MP2)XK-inspired composite wavefunction methods parametrized against large and chemically diverse training sets: Are they more accurate and/or robust than double hybrid DFT?
• Exploring Avenues Beyond Revised DSD Functionals: II. Random-Phase Approximation and scaled MP3 corrections
• Canonical and DLPNO-based composite wavefunction methods parametrized against large and chemically diverse training sets. 2. Correlation consistent basis sets, core-valence correlation, and F12 alternatives
• An Exchange-Based Diagnostic for Static Correlation

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