| Autor: |
Van Genechten, Karin A., Mortier, Wilfried J., Geerlings, Paul |
| Předmět: |
|
| Zdroj: |
Journal of Chemical Physics; 5/1/1987, Vol. 86 Issue 9, p5063, 9p |
| Abstrakt: |
The charge-dependent ‘‘effective’’ electronegativity χα of an atom α in a molecule or crystal, i.e., χα=(χ0α+Δχα)+2(η0α +Δηα)qα +∑β≠α qβ/Rαβ differs from the expression for the isolated atom (χ0α+2η0αqα) because of corrections to the electronegativity (Δχα) and hardness (Δηα), respectively, and due to the external potential generated by the surrounding charges qβ at distances Rαβ (new quantum-mechanical proof given). After calibration of Δχα and Δηα for all atom types, ab initio charges can be reproduced to within a few hundredths of an electron by the electronegativity equilization method (using χav=χα=χβ··· and ∑β qβ=constant). Application of this algorithm to the solid state (i.e., charges and external potential being generated in a self-consistent way and using Ewald’s method for determining the Madelung potential) leads to a novel method for determining ‘‘ab initio quality’’ charges and the value of the average electronegativity. If applied to SiO2 polymorphs, a relation between the refractive index and the average electronegativity is discovered, indicating for the first time quantitatively the importance of the structure type for the charge distribution and the average electronegativity in particular, and for the electronic properties in general. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
|
