Relevance of the slowly varying electron gas to atoms, molecules, and solids.
We present a Thomas-Fermi-inspired density scaling under which electron densities of atomic, molecular, or condensed matter become both large and slowly varying, so that semiclassical approximations and second-order density gradient expansions are asymptotically exact for the kinetic and exchange energies. Thus, even for atoms and molecules, density-functional approximations should recover the universal second-order gradient expansions in this limit. We also explain why common generalized gradient approximations for exchange do not.
Perdew
John P
JP
Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118, USA.
Constantin
Lucian A
LA
Sagvolden
Espen
E
Burke
Kieron
K