Electrostatic force theory for a molecule and interacting molecules. I. Concept and illustrative applications
Electrostatic force theory for a molecule and interacting molecules. I. Concept and illustrative applications
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分子和相互作用分子的静电力理论。
DOI：
10.1021/ja00783a008
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发表时间：
1973
影响因子：
15
通讯作者：
H. Nakatsuji
中科院分区：
文献类型：
--
作者：
H. Nakatsuji
提出了静电力（ESF）理论，在赫尔曼和费曼的静电定理的基础上，通过力的概念（而不是通过能量学）来研究化学现象。利用该定理的物理简单性和直观性，我们导出了三个图形概念，称为原子偶极子（AD）力、交换（EC）力和总电荷（GC）力。 AD力代表相关原子核A和属于原子A的AO的极化电子分布的加权中心之间的吸引力。EC力代表原子核A和通过电子交换堆积在原子核A和其相邻原子B之间区域的电子分布之间的吸引力。 GC力代表原子核A和原子B上的总电荷之间的静电相互作用。这些力在通常分子中的相对重要性是AD力> EC力（三键>双键>单键）55>GC力。 AD 力对于孤对电子很重要，EC 力取决于键的多重性。为了将该理论的适用性扩展到多种分子，还研究了原子 A 和取代基 B 的变化对这些力的影响。还讨论了随着电子结构的变化（例如，通过电子激发、电离、电子附着等）这些力的变化。由此，可以获得关于常见分子形状的简单定性测量。一些说明性的例子展示了 ESF 理论在预测基态和激发态分子形状以及理解化学反应和产物结构的本质方面实际上是如何发挥作用的。目前的理论概念已被证明足够广泛，能够应用于化学中的这两个基本问题。
The electrostatic force (ESF) theory in which chemical phenomena are studied through the force concept (not through energetics) on the basis of the electrostatic theorem of Hellmann and Feynman is presented. Taking advantage of the physical simplicity and visuality of this theorem, we derived three pictorial concepts called atomic dipole (AD) force, exchange (EC) force, and gross charge (GC) force. The AD force represents the attraction between the concerned nucleus A and the weighted center of the polarized electron distribution belongingto the AO’s of atom A. The EC forcerepresents the attraction between nucleus A and the electron distribution piled up in the regionbetween nucleus A and its neighboring atom B through electron exchange. The GC forcerepresents the electrostatic interaction between nucleus A and the gross charge on atom B. The relative importance of these forces in usualmolecules is AD force> EC force (triple> double> single bond) 55> GC force. The AD force is important for lone-pair electrons, and the EC force depends on bond multiplicity. In order to extend the applicability of the theory to a wide variety of molecules, the influences induced on these forces by the changes of atom A and substituent B are also studied. The change in these forces following the change in electronic structure (eg, by electron excitation, ionization, electron attachment, etc.) is also discussed. From these, a simple qualitative measure about the shapes of usual molecules is obtained. For some illustrative examples it is shown how the ESF theory works actually in predicting shapes of molecules in boththe ground and excited states and in understanding natures of chemical reactions and structures of products. The present theoretical concept is shown to be wide enough to be able to apply to both of these fundamental problems in chemistry.