Convergence of coupled cluster perturbation theory

Abstract

The convergence of a recently proposed coupled cluster (CC) family of perturbation series [Eriksen, J. J. et al., J. Chem. Phys. 140, 064108 (2014)], in which the energetic difference between two CC models - a low-level parent and a high-level target model - is expanded in orders of the Møller-Plesset (MP) fluctuation potential, is investigated for four prototypical closed-shell systems (Ne, singlet methylene, distorted HF, and the fluoride anion) in standard and augmented basis sets. In these investigations, energy corrections of the various series have been calculated to high orders and their convergence radii determined by probing for possible front- and back-door intruder states, the existence of which would make the series divergent. In summary, we conclude how it is primarily the choice of target state, and not the choice of parent state, which ultimately governs the convergence behavior of a given series. For example, restricting the target state to, say, triple or quadruple excitations might remove intruders present in series that target the full configuration interaction (FCI) limit, such as the standard MP series. Furthermore, we find that whereas a CC perturbation series might converge within standard correlation consistent basis sets, it may start to diverge whenever these become augmented by diffuse functions, similar to the MP case. However, unlike for the MP case, such potential divergences are not found to invalidate the practical use of the low-order corrections of the CC perturbation series.