Automatic Orbital Pair Selection for Multilevel Local Coupled-Cluster Based on Orbital Maps.

Abstract

We present an automatic, orbital-map based orbital-pair selection scheme for multilevel local coupled-cluster approaches that exploits the locality of chemical reactions by focusing on the part of the molecule directly involved in the reaction. The previously introduced pair-selected multilevel extension to domain-based local pair natural orbital coupled-cluster with singles, doubles, and semicanonical perturbative triples [DLPNO-CCSD(T0)] partitions the orbital pairs according to relative changes in pair correlation energies [Bensberg, M.; Neugebauer, J. Orbital pair selection for relative energies in the domain-based local pair natural orbital coupled-cluster method. J. Chem. Phys. 2022, 157, 064102. 10.1063/5.0100010]. To this end, maps between localized orbitals are required which in turn require maps between the atoms of structures along reaction paths. So far, these atom maps have been manually determined, which can be a (human) time-consuming procedure. Here, we present an automatic atom mapping algorithm based on the principle of minimum chemical distance that incorporates orientation dependence through dihedral angles. A similar strategy is then introduced to obtain orbital maps, which proves advantageous over the previously used direct orbital selection. Along with a modified orbital pair prescreening, this results in an improved variant of the pair-selected multilevel DLPNO-CCSD(T0) method. The performance of this approach is demonstrated for various reaction types showing a significant efficiency gain and accurate results due to beneficial, systematic error cancellation. The presented method operates in a black-box manner due to its fully automatized algorithms with only the need to specify a single target-accuracy parameter. Additionally, we demonstrate that basis set extrapolation techniques can be applied. In this context, the approach shows deficiencies for the use of large basis sets, especially with diffuse basis functions, which can be traced back to the semicanonical triples correction.