Performance of Localized Coupled Cluster Methods in a Moderately Strong Correlation Regime: Hückel-Möbius Interconversions in Expanded Porphyrins

Abstract

Localized orbital coupled cluster theory has recently emerged as an nonempirical alternative to DFT for large systems. Intuitively, one might expect such methods to perform less well for highly delocalized systems. In the present work, we apply both canonical CCSD(T) and a variety of localized approximations thereto to a set of expanded porphyrins -- systems that can switch between Hückel, figure-eight, and Möbius topologies under external stimuli. Both minima and isomerization transition states are considered. We find that Möbius(-like) structures have much stronger static correlation character than the remaining structures, and that this causes significant errors in DLPNO-CCSD(T) and even DLPNO-CCSD(T1) approaches, unless TightPNO cutoffs are employed. If sub-kcal/mol reproduction of canonical relative energies is required even for Möbius-type systems (or other systems plagued by strong static correlation), then Nagy and Kallay's LNO-CCSD(T) method with "tight" settings can provide that, at much greater computational expense than either the PNO-LCCSD(T) or DLPNO-LCCSD(T) approaches but with still a much gentler CPU time scaling than canonical approaches. We would propose the present POLYPYR21 dataset as a benchmark for localized orbital methods, or more broadly, for the ability of lower-level methods to handle energetics with strongly varying degrees of static correlation.

arXiv comment27 pages; revised version. J. Chem. Theory. Comput., ASAP (2020)

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