Density functional theory is straying from the path toward the exact functional

Abstract

Whither the density in DFT calculations? The continuing development of density functional theory (DFT) has greatly expanded the size and complexity of molecules amenable to computationally tractable simulation. The conventional metric of success for new functionals has been the accuracy of their calculated energies. Medvedev et al. examined how well these functionals calculate electron density across a series of neutral and cationic atoms (see the Perspective by Hammes-Schiffer). Although historically the accuracies of energy and density have improved in tandem, certain recent functionals have sacrificed fidelity to the true density. Science , this issue p. 49 ; see also p. 28