Cluster perturbation theory. IV. Convergence of cluster perturbation series for energies and molecular properties

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The theoretical foundation has been developed for establishing whether cluster perturbation (CP) series for the energy, molecular properties, and excitation energies are convergent or divergent and for using a two-state model to describe the convergence rate and convergence patterns of the higher-order terms in the CP series. To establish whether the perturbation series are convergent or divergent, a fictitious system is introduced, for which the perturbation is multiplied by a complex scaling parameter z. The requirement for convergent perturbation series becomes that the energy or molecular property, including an excitation energy, for the fictitious system is an analytic, algebraic function of z that has no singularities when the norm |z| is smaller than one. Examples of CP series for the energy and molecular properties, including excitation energies, are also presented, and the two-state model is used for the interpretation of the convergence rate and the convergence patterns of the higher-order terms in these series. The calculations show that the perturbation series effectively become a two-state model at higher orders.

Original languageEnglish
Article number134111
JournalThe Journal of Chemical Physics
Volume150
Issue13
Number of pages22
ISSN0021-9606
DOIs
Publication statusPublished - 2019

    Research areas

  • BASIS-SETS, DIVERGENCE, NEON, PLESSET, SPACE

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