Bypassing the Energy Functional in Density Functional Theory: Direct Calculation of Electronic Energies from Conditional Probability Densities

Abstract

Density functional calculations can fail for want of an accurate exchange-correlation approximation. The energy can instead be extracted from a sequence of density functional calculations of conditional probabilities (CP DFT). Simple CP approximations yield usefully accurate results for two-electron ions, the hydrogen dimer, and the uniform gas at all temperatures. CP DFT has no self-interaction error for one electron, and correctly dissociates H_{2}, both major challenges. For warm dense matter, classical CP DFT calculations can overcome the convergence problems of Kohn-Sham DFT.