Adventures in DFT by a wavefunction theorist.

Abstract

The attraction density functional theory (DFT) has for electronic structure theory is that it is easier to do computationally than ab initio, correlated wavefunction methods, due to its effective one-particle structure. On the contrary, ab initio theorists insist on the ability to converge to the right answer in appropriate limits, but this requires a treatment of the reduced two-particle density matrix. DFT avoids that by appealing to an "existence" theorem (not a constructive one) that all its effects are subsummed into a DFT functional of the one-particle density. However, the existence of thousands of DFT functionals emphasizes that there is no satisfactory way to systematically improve the Kohn-Sham (KS) version as most changes in parameterization or formulation seldom lead to a new functional that is genuinely better than others. Some researchers in the DFT community try to address this issue by imposing conditions rigorously derived from exact DFT considerations, but to date, no one has shown how this route will ever lead to converged results even for the ground state, much less for all the other electronic states obtained from time-dependent DFT that are critically important for chemistry. On the contrary, coupled-cluster (CC) theory and its equation-of-motion extensions provide rigorous results for both that KS-DFT methods are attempting to emulate. How to use them and their exact formal properties to tie CC theory to an effective one-particle form is the target of this perspective. This route addresses the devil's triangle of KS-DFT problems: the one-particle spectrum, self-interaction, and the integer discontinuity.