Atomic charges were investigated as functions of detectable atomic and molecular constants at equilibrium structures. It was found based upon the variation idea that atomic charges in highly ionic molecules can be expressed as a function of molecular dipole moments, polarizabilities of free cations, and polarizabilities of free neutral atoms of the corresponding anions. The function can be given in the form of classical Rittner’s relationship (J. Chem. Phys. 1951, 19, 1030). For the ground states of alkali halide molecules, the predicted atomic charges are close to an elementary charge e and the predicted dipole moments are in good agreement with the observed values; for spin-restricted high-ionic systems such as the lowest ⁹Σ electronic states of BN, AlN, GaN, BP, AlP, GaP, BAs, AlAs, and GaAs molecules, the predicted atomic charges are also near 1e and in good agreement with the results of natural population analysis at MRCI/cc-pvqz and HF/6-311+G(3df) levels. Polarizabilities for the lowest quintet states of B^–, Al^–, Ga^–, N⁺, P⁺, and As⁺ ions were also obtained based upon high-level ab initio computations. Atomic charges from other related methods are also investigated for comparison. The results demonstrate that high-quality atomic charges can be obtained with detectable variables, such as molecular dipole moment, vibrational frequency, as well as polarizabilities of the related free atoms and ions.

中文翻译：

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高离子双原子分子中的原子电荷

研究了原子电荷与平衡结构中可检测到的原子和分子常数的关系。基于变体思想发现，高离子分子中的原子电荷可以表示为分子偶极矩，游离阳离子的极化率和相应阴离子的游离中性原子的极化率的函数。功能可以在古典Rittner的关系（的形式给出J.化学物理。1951，19，1030）。对于碱金属卤化物分子的基态，预测的原子电荷接近于基本电荷e，并且预测的偶极矩与观测值高度吻合。适用于自旋受限的高离子系统，例如最低的^9个ΣBN，氮化铝，氮化镓，BP，ALP，的GaP，BAS，的AlAs和GaAs分子的电子态，预测的原子电荷也接近1个Ë并与自然群体分析中的MRCI / CC-的结果吻合良好pvqz和HF / 6-311 + G（3df）的水平。极化为B的最低五重峰态^- ，铝^- ，镓^-，N ⁺，P ⁺和As ⁺还可以根据高级从头算算获得离子。还研究了其他相关方法的原子电荷以进行比较。结果表明，可以通过可检测的变量获得高质量的原子电荷，例如分子偶极矩，振动频率以及相关自由原子和离子的极化率。