Steric effect: a quantitative description from density functional theory.

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.