Noorizadeh Siamak, Shakerzadeh Ehsan
Chemistry Department, College of Sciences, Shahid Chamran University, Ahwaz, Iran.
J Phys Chem A. 2008 Apr 17;112(15):3486-91. doi: 10.1021/jp709877h. Epub 2008 Mar 11.
By calculating the energies of neutral and different ionic forms (M2+, M+, M, M-, and M2-) of 32 elements (using B3LYP/6-311++G** level of theory) and taking energy (E) to be a Morse-like function of the number of electrons (N), the electrophilicity values (omega) are calculated for these atoms. The obtained electrophilicities show a good linearity with some commonly used electronegativity scales such as Pauling and Allred-Rochow. Using these electrophilicities, the ionicities of some diatomic molecules are calculated, which are in good agreement with the experimental data. Therefore, these electrophilicities are introduced as a new scale for atomic electronegativity, chi(omega)0. The same procedure is also performed for some simple polyatomic molecules. It is shown that the new scale successfully obeys Sanderson's electronegativity equalization principle and for those molecules which have the same number of atoms, the ratio of the change in electronegativity during the formation of a molecule from its elements to the molecular electronegativity (Delta chi/chi omega) is the same.
通过计算32种元素的中性及不同离子形式（M2 +、M +、M、M -和M2 -）的能量（使用B3LYP/6 - 311++G**理论水平），并将能量（E）作为电子数（N）的类莫尔斯函数，计算了这些原子的亲电性值（ω）。所得亲电性与一些常用的电负性标度（如鲍林标度和阿尔德 - 罗周标度）呈现出良好的线性关系。利用这些亲电性，计算了一些双原子分子的离子性，其与实验数据吻合良好。因此，引入这些亲电性作为一种新的原子电负性标度χ(ω)0。对一些简单的多原子分子也进行了同样的操作。结果表明，新标度成功遵循桑德森电负性均衡原理，对于那些原子数相同的分子，从其元素形成分子过程中电负性的变化与分子电负性之比（Δχ/χω）是相同的。
