Correlation regions within a localized molecular orbital approach

Abstract

A hybrid scheme for the computation of reaction energies in large molecular systems is proposed. The approach is based on localized orbitals and allows for the treatment of different parts of a molecule at different computational levels. The localized orbitals are assigned to regions, and then different local correlation methods, such as local MP2 or local CCSD(T), can be applied to different regions. In contrast to previous hybrid schemes, the molecule does not have to be split into parts and, therefore, it is not necessary to saturate dangling bonds using link atoms. For fixed region sizes, the cost of the high-level calculation becomes independent of the molecular size, and it is demonstrated that 𝒪(1) scaling can be achieved. Illustrative applications are presented and the convergence of the results with respect to the size of the regions is investigated for reaction energies, barrier heights, and weakly bound complexes.