Surprising cases of divergent behavior in Mo/ller–Plesset perturbation theory

Abstract

High‐order Mo/ller–Plesset perturbation calculations have been carried out for several small molecules and compared to full configuration interaction (FCI) results. The convergence of the Mo/ller–Plesset series is found to depend crucially on the one‐electron basis sets. Addition of diffuse basis functions leads in some cases to divergent behavior of the Mo/ller–Plesset series, even for highly single reference dominated systems as Ne and HF. The results thus questions the usefulness of higher‐order perturbation calculations as a vehicle for obtaining arbitrary accuracy of quantum chemical calculations and raises the fundamental theoretical question: When does Mo/ller–Plesset perturbation theory converge for many‐electron systems in extended basis sets?