Discrete and Continuous Dynamical Systems - Series A (DCDS-A)

Understanding Thomas-Fermi-Like approximations: Averaging over oscillating occupied orbitals

Pages: 5319 - 5325, Volume 33, Issue 11/12, November/December 2013      doi:10.3934/dcds.2013.33.5319

       Abstract        References        Full Text (258.5K)       Related Articles       

John P. Perdew - Department of Physics and Quantum Theory Group, Tulane University, New Orleans, LA 70123, United States (email)
Adrienn Ruzsinszky - Department of Physics and Quantum Theory Group, Tulane University, New Orleans, LA 70123, United States (email)

Abstract: The Thomas-Fermi equation arises from the earliest density functional approximation for the ground-state energy of a many-electron system. Its solutions have been carefully studied by mathematicians, including J.A. Goldstein. Here we will review the approximation and its validity conditions from a physics perspective, explaining why the theory correctly describes the core electrons of an atom but fails to bind atoms to form molecules and solids. The valence electrons are poorly described in Thomas-Fermi theory, for two reasons: (1) This theory neglects the exchange-correlation energy, ``nature's glue". (2) It also makes a local density approximation for the kinetic energy, which neglects important shell-structure effects in the exact kinetic energy that are responsible for the structure of the periodic table of the elements. Finally, we present a tentative explanation for the fact that the shell-structure effects are relatively unimportant for the exact exchange energy, which can thus be more usefully described by a local density or semilocal approximation (as in the popular Kohn-Sham theory): The exact exchange energy from the occupied Kohn-Sham orbitals has an extra sum over orbital labels and an extra integration over space, in comparison to the kinetic energy, and thus averages out more of the atomic individuality of the orbital oscillations.

Keywords:  Thomas-Fermi, kinetic energy, exchange energy, averaging, density functional.
Mathematics Subject Classification:  41, 45, 46, 49, 81.

Received: December 2011;      Available Online: May 2013.