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 H2, both major challenges. For warm dense matter, classical CP-DFT calculations can overcome the convergence problems of Kohn-Sham DFT.

arXiv comment6 pages, 3 figures, 2 tables

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• Metadensity functional learning for classical fluids: Regularizing with pair correlations
• Correlation energy of the uniform gas determined by ground state conditional probability density functional theory
• Coupling-Constant Averaged Exchange-Correlation Hole for He, Li, Be, N, Ne Atoms from CCSD
• On the Geometric Potential and the Relationship between the Exact Electron Factorization and Density Functional Theory