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.

Surprising cases of divergent behavior in Møller-Plesset perturbation theory

Koch, Henrik;
1996

Abstract

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.
Physics and Astronomy (all); Physical and Theoretical Chemistry
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11384/69969
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