Surprising cases of divergent behavior in Møller-Plesset perturbation theory

High-order Møller-Plesset perturbation calculations have been carried out for several small molecules and compared to full configuration interaction (FCI) results. The convergence of the Møller-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 Møller-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 Møller-Plesset perturbation theory converge for many-electron systems in extended basis sets? © 1996 American Institute of Physics.