Convergence of coupled cluster perturbation theory.

Abstract

The convergence of a recently proposed coupled cluster (CC) family of perturbation series [J. J. Eriksen 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 CH2, distorted HF, and F-) 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 have been 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 the target state, and not the choice of the 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 which target the full configuration interaction 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.