On the foundations of chemical reactivity theory.

In formulating chemical-reactivity theory (CRT) so as to give it a deep foundation in density-functional theory (DFT), Parr, his collaborators, and subsequent workers have introduced reactivity indices as properties of isolated reactants, some of which are in apparent conflict with the underlying DFT. Indices which are first derivatives with respect to electron number are staircase functions of number, making electronegativity equalization problematic. Second derivative indices such as hardness vanish, putting hardness-based principles out of reach. By reformulating CRT within our partition theory, which provides an exact decomposition of a system into its component species, we resolve the conflict. We show that the reactivity of a species depends on its chemical context and define that context. We establish when electronegativity equalization holds and when it fails. We define a generalization of hardness, a hardness matrix containing the self-hardness of the individual species and the mutual hardnesses of the pairs of species of the system, and identify the physical origin of hardness. We introduce a corresponding generalization of the Fukui function as well as of the local and global softnesses and the softness kernel of the earlier formulation. We augment our previous formulation of the partition theory by introducing a model energy function and express the difference between the exact and the model forces on the nuclei in terms of the new reactivity indices. For simplicity, our presentation is limited to time-reversal invariant systems with vanishing spin density; it is straightforward to generalize the theory to finite spin density.