Properties of the density functional response kernels and its implications on chemistry

An overview of mathematical properties of the non-local second order derivatives of the canonical, grand canonical, isomorphic, and grand isomorphic ensembles is given. The significance of their positive or negative semidefiniteness and the implications of these properties for atoms and molecules are discussed. Based on this property, many other interesting properties can be derived, such as the expansion in eigenfunctions, bounds on the diagonal and off-diagonal elements, and the eigenvalues of these kernels. We also prove Kato's theorem for the softness kernel and linear response and the dissociation limit of the linear responses as the sum of the linear responses of the individual fragments when dissociating a system into two non-interacting molecular fragments. Finally, strategies for the practical calculation of these kernels, their eigenfunctions, and their eigenvalues are discussed. Published under an exclusive license by AIP Publishing.

Automated summary

This article provides an overview of the mathematical properties of non-local second order derivatives in various ensembles and discusses their significance for atoms and molecules. The article also explores other interesting properties derived from these properties and proposes practical strategies for calculating these kernel functions and their eigenvalues.