Constraining density functional approximations to yield self-interaction free potentials

Abstract

Self-interactions (SIs) are a major problem in density functional approximations and the source of serious divergence from experimental results. Here, we propose to optimize density functional total energies in terms of the effective local potential, under constraints for the effective potential that guarantee it is free from SI errors and consequently asymptotically correct. More specifically, we constrain the Hartree, exchange and correlation potential to be the electrostatic potential of a non-negative effective repulsive density of $N-1$ electrons. In this way, the optimal effective potentials exhibit the correct asymptotic decay, resulting in significantly improved one-electron properties.

References in corpus (5)

• Efficient atomic self-interaction correction scheme for non-equilibrium quantum transport
• Avoiding Unbound Anions in Density Functional Calculations
• Electrical response of molecular systems: the power of self-interaction corrected Kohn-Sham theory
• Prediction of the derivative discontinuity in density functional theory from an electrostatic description of the exchange and correlation potential
• Nonanalyticity of the optimized effective potential with finite basis sets

Cited by in corpus (24)

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• Density-inversion method for the Kohn-Sham potential: role of the screening density
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• Effect of ensemble generalization on the highest-occupied Kohn-Sham eigenvalue
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• First-principles derivation and properties of density-functional average-atom models
• Quasi-particle energy spectra in local reduced density matrix functional theory
• Improved calculations of mean ionization states with an average-atom model
• Orbitals from local RDMFT: Are they Kohn-Sham or Natural Orbitals?
• Performance of the Constrained Minimization of the Total Energy in Density Functional Approximations: the Electron Repulsion Density and Potential
• Improving the exchange and correlation potential in density functional approximations through constraints
• Generalised Kohn-Sham equations with accurate total energy and single-particle eigenvalue spectrum
• Local Exchange-Correlation Potentials by Density Inversion in Solids
• Density functionals with spin-density accuracy for open shells
• Effective local potentials for density and density-matrix functional approximations with non-negative screening density