Liu Shubin
The Renaissance Computing Institute (RENCI), University of North Carolina, Chapel Hill, North Corolina 27599-3420, USA.
J Chem Phys. 2007 Jun 28;126(24):244103. doi: 10.1063/1.2747247.
The concepts of steric energy, steric potential, and steric charge are introduced within the density functional theory framework. The steric energy, representing a hypothetical state with all electrons packed into the lowest orbital and other effects entirely excluded, is a measure of the intrinsic space occupied by an electronic system. It is exclusive, repulsive, and extensive, and it vanishes for homogeneous electron gas. When Bader's zero-flux boundary condition is adopted, atoms in molecules are found to achieve balanced steric repulsion among one another with vanished steric energy density interfaces. A few molecular systems involving conformation changes and chemical reactions have been investigated to examine the relative contribution of the steric and other effects, providing insights for a few controversial topics from a different perspective.
在密度泛函理论框架内引入了空间能、空间势和空间电荷的概念。空间能代表一种假设状态，其中所有电子都被填充到最低轨道且完全排除其他效应，它是电子系统占据的固有空间的一种度量。它具有排他性、排斥性且是广延量，对于均匀电子气它为零。当采用巴德的零通量边界条件时，发现分子中的原子通过空间能密度界面消失来实现彼此间的平衡空间排斥。已经研究了一些涉及构象变化和化学反应的分子系统，以检验空间效应和其他效应的相对贡献，从不同角度为一些有争议的话题提供了见解。
