On the nature of the Møller-Plesset critical point

Alexey V. Sergeev, David Z. Goodson, Steven E. Wheeler, Wesley D. Allen

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

It has been suggested [F. H. Stillinger, J. Chem. Phys. 112, 9711 (2000)] that the convergence or divergence of Møller-Plesset perturbation theory is determined by a critical point at a negative value of the perturbation parameter z at which an electron cluster dissociates from the nuclei. This conjecture is examined using configuration-interaction computations as a function of z and using a quadratic approximant analysis of the high-order perturbation series. Results are presented for the He, Ne, and Ar atoms and the hydrogen fluoride molecule. The original theoretical analysis used the true Hamiltonian without the approximation of a finite basis set. In practice, the singularity structure depends strongly on the choice of basis set. Standard basis sets cannot model dissociation to an electron cluster, but if the basis includes diffuse functions then it can model another critical point corresponding to complete dissociation of all the valence electrons. This point is farther from the origin of the z plane than is the critical point for the electron cluster, but it is still close enough to cause divergence of the perturbation series. For the hydrogen fluoride molecule a critical point is present even without diffuse functions. The basis functions centered on the H atom are far enough from the F atom to model the escape of electrons away from the fluorine end of the molecule. For the Ar atom a critical point for a one-electron ionization, which was not previously predicted, seems to be present at a positive value of the perturbation parameter. Implications of the existence of critical points for quantum-chemical applications are discussed.

Original languageEnglish
Article number064105
JournalJournal of Chemical Physics
Volume123
Issue number6
DOIs
Publication statusPublished - 8 Aug 2005
Externally publishedYes

Fingerprint

critical point
Electrons
Hydrofluoric Acid
perturbation
Atoms
hydrofluoric acid
electrons
Molecules
atoms
divergence
dissociation
molecules
Hamiltonians
Fluorine
configuration interaction
escape
Ionization
fluorine
perturbation theory
valence

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Sergeev, A. V., Goodson, D. Z., Wheeler, S. E., & Allen, W. D. (2005). On the nature of the Møller-Plesset critical point. Journal of Chemical Physics, 123(6), [064105]. https://doi.org/10.1063/1.1991854

On the nature of the Møller-Plesset critical point. / Sergeev, Alexey V.; Goodson, David Z.; Wheeler, Steven E.; Allen, Wesley D.

In: Journal of Chemical Physics, Vol. 123, No. 6, 064105, 08.08.2005.

Research output: Contribution to journalArticle

Sergeev, AV, Goodson, DZ, Wheeler, SE & Allen, WD 2005, 'On the nature of the Møller-Plesset critical point', Journal of Chemical Physics, vol. 123, no. 6, 064105. https://doi.org/10.1063/1.1991854
Sergeev AV, Goodson DZ, Wheeler SE, Allen WD. On the nature of the Møller-Plesset critical point. Journal of Chemical Physics. 2005 Aug 8;123(6). 064105. https://doi.org/10.1063/1.1991854
Sergeev, Alexey V. ; Goodson, David Z. ; Wheeler, Steven E. ; Allen, Wesley D. / On the nature of the Møller-Plesset critical point. In: Journal of Chemical Physics. 2005 ; Vol. 123, No. 6.
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