PROPERTIES OF ATOMS IN MOLECULES - ADDITIVITY AND TRANSFERABILITY OF GROUP POLARIZABILITIES
PROPERTIES OF ATOMS IN MOLECULES - ADDITIVITY AND TRANSFERABILITY OF GROUP POLARIZABILITIES
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DOI：
10.1080/00268979200100901
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发表时间：
1992-04-10
影响因子：
1.7
通讯作者：
LAIDIG, KE
中科院分区：
文献类型：
--
作者：
BADER, RFW;KEITH, TA;LAIDIG, KE
碳氢化合物中基团性质的可加性和可转移性的实验证明，即它们的摩尔体积、极化率和生成热的可加性方案的建立，在建立化学中官能团的概念方面发挥了核心作用。它示出在这里，在分子中的原子的理论恢复和解释实验观察到的加和性和可转移性的基团的极化率在烃类，就像以前已经做的热的形成，电矩和摩尔体积。所有群体属性都表现出相同的可转移行为模式。特别是，基团极化率和相应的基团体积之间的线性关系，如理论所定义的，使人们能够预测烃的平均极化率，以更好地使用容易计算的基团体积的百分之一半。氢原子电荷密度的外层鞘层在外场方向上极化，而碳原子密度表现出相反的极化。的极化率张量的纵向分量的增加与链长的增加所示的产生从场诱导的电荷转移的长度的分子。本文证明了量子力学预测分子中原子的性质，就像它预测分子本身的性质一样，即使在外场存在的情况下。
The experimental demonstration of the additivity and transferability of group properties in the hydrocarbons, that is, the establishment of additivity schemes for their molar volumes, polarizabilities and heats of formation, played a central role in establishing the concept of a functional group in chemistry. It is shown here that the theory of atoms in molecules recovers and explains the experimentally observed additivity and transferability of the group polarizabilities in the hydrocarbons, just as has been previously done for the heats of formation, electric moments and molar volumes. All of the group properties exhibit the same pattern of transferable behavior. In particular, the linear relationship between the group polarizabilities and corresponding group volumes, as defined by theory, enable one to predict the mean polarizabilities of hydrocarbons to better than one-half of one percent using readily calculated group volumes. The outer sheath of hydrogen atom charge density polarizes in the direction of the external field, while the carbon atom densities exhibit an opposing polarization. The increase in the longitudinal component of the polarizability tensor with increasing chain length is shown to arise from a field-induced transfer of charge over the length of the molecule. This paper demonstrates that quantum mechanics predicts the properties of an atom in a molecule just as it does those of the molecule itself, even in the presence of an external field.