The reliability of the point charge model representing intermolecular effects in ab initio calculations

P. Surján, János G. Ángyán

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The reliability of modeling ions or polar molecules by point charges is investigated from the point of view of possible non-physical variational distortions of the molecular wavefunction. Mathematical and observable-based criteria are given to monitor the extent of variational distortions. A model system of two H2molecules and a cation is studied, allowing investigation of large basis sets. The unphysical distortion, which tends to be worse as the basis set increases, is already observed in split-shell quality bases, if sensitive parameters (e.g. van der Waals distances) are investigated. It has a negligible influence on less sensitive molecular properties, such as the total electron density, even in large basis sets.

Original languageEnglish
Pages (from-to)258-264
Number of pages7
JournalChemical Physics Letters
Volume225
Issue number1-3
DOIs
Publication statusPublished - Jul 29 1994

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molecular properties
Wave functions
Carrier concentration
Cations
Ions
cations
Molecules
molecules
ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Surfaces and Interfaces

Cite this

The reliability of the point charge model representing intermolecular effects in ab initio calculations. / Surján, P.; Ángyán, János G.

In: Chemical Physics Letters, Vol. 225, No. 1-3, 29.07.1994, p. 258-264.

Research output: Contribution to journalArticle

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