Issues and challenges in orbital-free density functional calculations

Solving the Euler equation which corresponds to the energy minimum of a density functional expressed in orbital-free form involves related but distinct computational challenges. One is the choice between allelectron and pseudopotential calculations and, if the latter, construction of the pseudopotential. Another is the stability, speed, and accuracy of solution algorithms. Underlying both is the fundamental issue of satisfactory quality of the approximate functionals (kinetic energy and exchange–correlation). We address both computational issues and illustrate them by some comparative performance testing of our recently developed modified-conjoint generalized gradient approximation kinetic energy functionals. Comparisons are given for atoms, diatomic molecules, and some simple solids. © 2012 Elsevier B.V. All rights reserved.