We illustrate the main features of a recently proposed method based on ensemble density functional theory to divide rigorously a complex molecular system into its parts (J. Phys. Chem. A 2007, 111, 2229). The illustrative system is an analog of the hydrogen molecule for which analytic expressions for the densities of the parts (hydrogen "atoms") are found along with the "partition potential" that enters the theory. While previous formulations of chemical reactivity theory lead to zero, or undefined, values for the chemical hardness of the isolated parts, we demonstrate they can acquire a finite and positive hardness within the present formulation.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry