Extrapolating the coupled-cluster sequence toward the full configuration-interaction limit

TLDR: In this article, the convergence of coupled-cluster energy sequences toward the full configuration interaction (FCI) limit is investigated for a variety of atoms and small molecules for which FCI energies are available, and the results are compared with those from Moller-Plesset perturbation theory.

Abstract: Extrapolation methods that accelerate the convergence of coupled-cluster energy sequences toward the full configuration–interaction (FCI) limit are developed and demonstrated for a variety of atoms and small molecules for which FCI energies are available, and the results are compared with those from Moller–Plesset (MP) perturbation theory. For the coupled-cluster sequence SCF, CCSD, CCSD(T), a method based on a continued-fraction formalism is found to be particularly successful. It yields sufficient improvement over conventional CCSD(T) that the results become competitive with, and often better than, results from the MP4-qλ method (MP4 summed with quadratic approximants and λ transformation). The sequence SCF, CCSD, CCSDT can be extrapolated with a quadratic approximant but the results are not appreciably more accurate than those from the CCSD(T) continued fraction. Singularity analysis of the MP perturbation series provides a criterion for estimating the accuracy the CCSD(T) continued fraction.