Regional virial in diatomic molecules

two criteria for defining zero-flux dividing surfaces

Vladimiro Mujica, M. García-Sucre, Y. Aray

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The dividing surfaces defining the regions where a variationally determined virial theorem holds can be taken as the surfaces through which the flux of the gradient of a scalar function that is different from the electronic density vanishes. Alternatively, real space can be partitioned through zero-flux surfaces of the gradient of the electronic density, a process which also renders fragments where the virial theorem holds. In the present study we examined the question of whether these two criteria are the same for very simple model wavefunctions for both homonuclear and heteronuclear diatomic molecules within the Born-Oppenheimer approximation. It was found that in the homonuclear case, which is essentially governed by the symmetry of the problem, the two criteria agree closely, the difference being in the curvature of the gradient contour lines. However, in the heteronuclear model, significant differences were found in both the curvature of the gradient contour lines and the shape of the dividing surface. The chemical and physical implications of these differences were analysed.

Original languageEnglish
Pages (from-to)125-134
Number of pages10
JournalJournal of Molecular Structure: THEOCHEM
Volume254
Issue numberC
DOIs
Publication statusPublished - Feb 12 1992

Fingerprint

diatomic molecules
Fluxes
gradients
virial theorem
Molecules
curvature
Born approximation
Born-Oppenheimer approximation
Wave functions
electronics
fragments
scalars
symmetry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

Regional virial in diatomic molecules : two criteria for defining zero-flux dividing surfaces. / Mujica, Vladimiro; García-Sucre, M.; Aray, Y.

In: Journal of Molecular Structure: THEOCHEM, Vol. 254, No. C, 12.02.1992, p. 125-134.

Research output: Contribution to journalArticle

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