Quantum topology. IV. Relation between the topological and energetic stabilities of molecular structures
Quantum topology. IV. Relation between the topological and energetic stabilities of molecular structures
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量子拓扑。
DOI：
10.1063/1.441725
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发表时间：
1981
影响因子：
4.4
通讯作者：
S. Anderson
中科院分区：
文献类型：
--
作者：
Y. Tal;R. Bader;T. Nguyen;M. Ojha;S. Anderson
研究了由电荷分布的拓扑性质决定的分子体系的结构稳定性和由势能超曲面的性质决定的同一体系的能量稳定性之间的关系。一般说来，人们可以将给定的分子结构与系统的能量稳定几何结构的开放邻域联系在一起。分子结构的变化是一个突然的过程，并给出了结构变化发生在过渡态几何构型附近的例子。这些观测表明，拓扑不稳定的结构对应于系统中能量不稳定的几何结构。根据Hellmann-Feynman定理，这种对应关系是合理的。Hellmann-Feynman定理将能量超曲面的梯度与电荷密度的梯度矢量场联系起来，该场的不稳定性决定了分子结构的不稳定性。
The relation between the structural stability of a molecular system as determined by the topological properties of its charge distribution and the energetic stability of the same system as determined by the properties of its potential energy hypersurface is studied. In general, it is found that one may associate a given molecular structure with an open neighborhood of an energetically stable geometry of the system. A change in molecular structure is an abrupt process, and examples are given in which the change in structure is found to occur in the immediate neighborhood of the transition state geometry. These observations suggest that topologically unstable structures correspond to energetically unstable geometries of a system. Such a correspondence can be rationalized in terms of the Hellmann–Feynman theorem which is shown to relate the gradients of the energy hypersurface to the gradient vector field of the charge density—the field whose instabilities determine the instabilities in molecular structure.