Using Pauli energy to appraise the quality of approximate semilocal non-interacting kinetic energy density functionals.

Abstract

It is well-known that the kinetic energy density (KED) functional is the most difficult to approximate in density functional theory (DFT), yet to take full advantage of DFT with its density-based descriptive capability of molecular properties, an accurate account of KED is a must. To have a better idea of how an approximate KED formula behaves and where we should focus in the future development of better approximate KEDs, in this work we propose to employ the Pauli energy to assess their quality. We tested the performance of a total of 22 approximate semilocal noninteracting KED functionals from the literature for 18 neutral atoms and 20 small molecules. We found that generalized gradient approximation formulas of the KED functional can often reasonably accurately predict the total kinetic energy value for atoms and molecules but failed miserably to forecast the integrated values for Pauli energy related properties. The reason behind this is that presently available approximate KED functionals are unable to accurately account for the kinetic energy distribution in the medium range away from nuclei, where the Pauli energy plays a crucial role. Our results strongly suggest that the key information missing in approximate KED functionals comes from the medium regions, not nuclear cusps nor asymptotic areas, and the Pauli energy is a reliable measure of the quality of approximate KED functionals. Future efforts in developing better KED approximations should be invested in the regions of molecules where chemical bonds are formed in order to accurately account for the Pauli energy.