An atomic charge study of highly ionic diatomic molecular systems
| Autor: | Roberto L. A. Haiduke, Daniel T. I. Nakazato, Eduardo L. de Sá |
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| Rok vydání: | 2009 |
| Předmět: |
Chemistry
Atoms in molecules Ionic bonding Condensed Matter Physics Diatomic molecule Atomic and Molecular Physics and Optics Dipole Physics::Atomic and Molecular Clusters Physics::Atomic Physics Physical and Theoretical Chemistry Atomic physics Anisotropy Mulliken population analysis Quantum CHELPG |
| Zdroj: | International Journal of Quantum Chemistry. 110:1729-1737 |
| ISSN: | 0020-7608 |
| DOI: | 10.1002/qua.22296 |
| Popis: | Four atomic charge formalisms are compared using highly ionic diatomic molecules, such as LiF, NaF, KF, LiCl, NaCl, KCl, BF, AlF, GaF, BeO, and MgO. All calculations were done at the QCISD/6-311G(2df) level. The only formalism consistent with the characteristics of all these systems is Quantum theory of atoms in molecules (QTAIM). Absolute Mulliken charge values are small. ChelpG charges are not reliable for systems in which the atoms are largely anisotropic. Generalized atomic polar tensor values are contaminated with charge fluxes and atomic dipole fluxes and fail when these contributions are important and do not cancel each other. Finally, the charge–charge flux–dipole flux model was applied to dipole moment derivatives with QTAIM. This analysis shows that charge flux and atomic dipole flux contributions during bond stretching are almost null, except for oxides. There are also evidences that the lone electron pair at Group 13 elements in fluorides becomes less localized as the bond is stretched. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 |
| Databáze: | OpenAIRE |
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