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首页> 外文期刊>Spectrochimica acta, Part A. Molecular and biomolecular spectroscopy >Factors affecting the relation between stretching frequencies and bond lengths. Diatomic and polyatomic species without adjustable fitting parameters
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Factors affecting the relation between stretching frequencies and bond lengths. Diatomic and polyatomic species without adjustable fitting parameters

机译:影响拉伸频率和键长之间关系的因素。双原子和多原子物种,没有可调的拟合参数

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In 76 sets of similar type bonds in species A(2), AB, AB(2), AB(3), and AB(4) the stretching frequency, v, is related to the bond length, r, by v = a/(r mu(1/2)) by where mu is the reduced mass. The sets treated include all ground states for which spectroscopic date were found for stable molecules, free radicals, carbenes and other species with unsatisfied valences, both ionic and covalent. The linear correlation coefficients of each set are always greater than 0.998. The slopes a and intercepts b are defined by the data of each set and vary widely. They become congruent, but not exactly identical, when a is multiplied by the square root of the mean value of the number of electrons in the valence shell of the two bonded atoms, the electrons that become joined in the molecular orbitals formed upon bonding. No adjustable parameters are used. The number of bonds treated, over 300, is not as important as the fact that all species found were treated. The aim is not to add yet another parametric correlation to the many extant, but to better understand the relation between these two fundamental properties of chemical bonds. (C) 2015 Elsevier B.V. All rights reserved.
机译:在物种A(2),AB,AB(AB)(2),AB(3)和AB(4)中的76组相似类型的键中,拉伸频率v与键长r相关,v = a /(r mu(1/2)),其中mu是减少的质量。处理的组包括所有基态,对于这些基态,发现了稳定的分子,自由基,卡宾和其他离子价和共价价不满意的物种的光谱数据。每组的线性相关系数始终大于0.998。斜率a和截距b由每组数据定义,并且变化很大。当a乘以两个键合原子的价壳中电子数的平均值的平方根时,它们变得完全一致,但并不完全相同,这些电子在键合时形成的分子轨道中结合在一起。没有使用可调参数。处理的键数超过300,并不像处理所有发现的物种那样重要。目的不是要在许多现有参数之间添加另一个参数相关性,而是要更好地理解化学键的这两个基本属性之间的关系。 (C)2015 Elsevier B.V.保留所有权利。

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