Visualization and analysis of the Kohn-Sham kinetic energy density and its orbital-free description in molecules (1508.03396v2)

Abstract: We visualize the Kohn-Sham kinetic energy density (KED), and the ingredients -- the electron density, its gradient and Laplacian -- used to construct orbital-free models of it, for the AE6 test set of molecules. These are compared to related quantities used in metaGGA's, to characterize two important limits -- the gradient expansion and the localized-electron limit typified by the covalent bond. We find the second-order gradient expansion of the KED to be a surprisingly successful predictor of the exact KED, particularly at low densities where this approximation fails for exchange. This contradicts the conjointness conjecture that the optimal enhancement factors for orbital-free kinetic and exchange energy functionals are identical. In addition we find significant problems with a recent metaGGA-level orbital-free KED, especially for regions of strong electron localization. We define an orbital-free description of electron localization and a revised metaGGA that improves upon atomization energies significantly.