Semilocal Kinetic Energy Density Functionals on Atoms and Diatoms

An accurate semilocal kinetic energy density functional (KEDF) is crucial for reliable orbital-free density functional theory calculations. In our study, we assessed the performance of representative semilocal KEDFs using a more stringent indicator. Our findings highlight the superiority of the Perdew-Constantin (PC) functional in delivering energies close to the reference values. Upon analysis of the PC functional, we identified that enhancing its performance can be achieved through a more effective region selection regime. Experimenting with various region selection indicators, we discovered that the Laplacian-dependent reduced density gradient proves to be helpful. Subsequently, we empirically constructed an augmented variant of the PC functional, which not only yields energies close to the references but also, more importantly, demonstrates qualitative predictions for stable molecules and provides reasonable quantitative estimates for bond lengths in diatomic systems.