Campero Antonio, Díaz Ponce Javier Alejandro
Departamento de Química, Chemistry Professor, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, Mexico City C.P. 09340, México.
Departamento de Física, Postdoctoral Position, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, Mexico City C.P. 09340, México.
ACS Omega. 2020 Oct 2;5(40):25520-25542. doi: 10.1021/acsomega.0c00256. eCollection 2020 Oct 13.
In this work, we propose a new representative electronegativity scale χ based on a statistical analysis of 11 electronegativity scales associated with electric ionic resonance energy, ionization potential, electron affinity, polarizability, electric force, average orbital energy, chemical potential, electrochemical reduction potential, and electric potential energy. Among these scales, it is the new PE° electronegativity scale, which relates the reduction potential ° to Pauling's electronegativity scale. The scale χ gives more weight to the physicochemical factors, which influence the electronegativity, but this scale is not necessarily the best electronegativity scale for the element. This scale is based on (1) the average of the experimental electronegativity values; (2) the proximity of an experimental value to the average given by the difference and the ratio to this average; (3) in critical cases, the periodicity network of the periods and the groups; and (4) the periodicity of the sequence of the ratios of the experimental electronegativity values to the best-selected electronegativity value. We have also taken as probe scales Nagle's, Allred and Rochow's, Allen's (Hoffman's and Politzer's), PE°, Gordy's, and Ghosh's electronegativity scales in order to investigate the trend of the physicochemical factors which influence the electronegativity. With this trend, we have determined zones where a physicochemical property influences the electronegativity more. We have also found that physicochemical perturbations such as the orbital overlap, the stable configurations, the nephelauxetic effect, the width of the band gap, the ligand field stabilization energy, the penetration of the orbitals, and the lattice energy influence the electronegativity. Besides, we have analyzed the exactness of the electronegativity of the scales through the periodical ranking, the chemical tripartite separation among ionic, covalent, or metallic bond (taking into account the amplitude of the metalloid band), and the physicochemical property of bond force. The representative χ electronegativity scale is the best in periodicity, followed by Batsanov's and Pauling's scales. In the type of chemical bond, the ranking depends on the number and kind of compounds in the sample, but in general, Pauling's, the ARS, and Batsanov's electronegativity scales are the best with a confidence interval of 95%. On the other hand, in the physical bond force, Batsanov's, Pauling's, Mulliken's, Nagle's, Allen's, the ARS, and the χ electronegativity scales are the best scales. Also, we have considered the free atom and the in situ hypotheses of electronegativity and used the low and high oxidation states to verify these hypotheses. Besides, as an example of the utility of this ranking of scales, we have analyzed the relation of lanthanum La and lutetium Lu to Group 3, lanthanides, and hafnium Hf. We also analyze the vertical, horizontal, Knight's move, and isodiagonal periodicity of the electronegativity and associate this periodicity to a similar chemical-physical behavior of elements or ions.
在这项工作中，我们基于对11种与电离子共振能、电离势、电子亲和势、极化率、电力、平均轨道能、化学势、电化学还原势和电势能相关的电负性标度的统计分析，提出了一种新的代表性电负性标度χ。在这些标度中，新的PE°电负性标度将还原电势°与鲍林电负性标度联系起来。标度χ对影响电负性的物理化学因素赋予了更大权重，但该标度不一定是元素的最佳电负性标度。此标度基于：（1）实验电负性值的平均值；（2）实验值与差值给出的平均值的接近程度以及与该平均值的比率；（3）在关键情况下，周期和族的周期性网络；（4）实验电负性值与最佳选择的电负性值的比率序列的周期性。我们还采用了纳格尔、奥尔雷德和罗周、艾伦（霍夫曼和波利策）、PE°、戈尔迪和戈什的电负性标度作为探测标度，以研究影响电负性的物理化学因素的趋势。根据这一趋势，我们确定了物理化学性质对电负性影响更大的区域。我们还发现，诸如轨道重叠、稳定构型、辅基效应、带隙宽度、配体场稳定能、轨道穿透和晶格能等物理化学扰动会影响电负性。此外，我们通过周期性排名、离子键、共价键或金属键之间的化学三分法分离（考虑类金属带的幅度）以及键力的物理化学性质，分析了这些标度电负性的准确性。代表性的χ电负性标度在周期性方面是最佳的，其次是巴萨诺夫标度和鲍林标度。在化学键类型方面，排名取决于样品中化合物的数量和种类，但总体而言，鲍林标度、ARS标度和巴萨诺夫电负性标度在95%的置信区间内是最佳的。另一方面，在物理键力方面，巴萨诺夫标度、鲍林标度、穆利肯标度、纳格尔标度、艾伦标度、ARS标度和χ电负性标度是最佳标度。此外，我们考虑了电负性的自由原子和原位假设，并使用低氧化态和高氧化态来验证这些假设。此外，作为这种标度排名实用性的一个例子，我们分析了镧La和镥Lu与第3族、镧系元素以及铪Hf的关系。我们还分析了电负性的垂直、水平、马步和等对角线周期性，并将这种周期性与元素或离子类似的化学 - 物理行为联系起来。
