Avoiding Unbound Anions in Density Functional Calculations

Abstract

Converged approximate density functional calculations usually do not bind anions, due to large self-interaction error. But Hartree-Fock calculations have no such prob- lem, producing negative HOMO energies. A recently proposed scheme for calculating DFT energies on HF densities is shown to work very well for molecules, better than the common practice of restricting the basis set, except for cases like CN, where the HF density is too inaccurate due to spin contamination.

Cited by in corpus (25)

• Perspective on density functional theory
• Understanding and reducing errors in density functional calculations
• The Importance of being consistent
• Ions in solution: Density Corrected Density Functional Theory (DC-DFT)
• Halogen Bonding Interactions: Revised Benchmarks and a New Assessment of Exchange vs. Dispersion
• Accurate Electron Affinities and Orbital Energies of Anions from a Non-Empirically Tuned Range-Separated Density Functional Theory Approach
• Reference electronic structure calculations in one dimension
• Donor and acceptor levels of organic photovoltaic compounds from first principles
• Constraining density functional approximations to yield self-interaction free potentials
• Strong-interaction limit of an adiabatic connection in Hartree-Fock theory
• Density Functional Resonance Theory of Unbound Electronic Systems
• Large coupling-strength expansion of the Møller-Plesset adiabatic connection: From paradigmatic cases to variational expressions for the leading terms
• Self-Interaction Correction in Water-Ion Clusters
• Energy Density Functionals From the Strong-Coupling Limit Applied to the Anions of the He Isoelectronic Series
• Effect of ensemble generalization on the highest-occupied Kohn-Sham eigenvalue
• Water mediated Electron Attachment to Nucleobases: Surface-bound vs Bulk Solvated Electrons
• Performance of a nonempirical exchange functional from the density matrix expansion: comparative study with different correlation
• Composition Dependence of the Charge Driven Phase Transition in Group-VI Transition Metal Dichalcogenides
• Electron attachment to Cytosine: The Role of Water
• Functional extrapolations to tame unbound anions in density-functional theory calculations
• Bypassing the energy functional in density functional theory: Direct calculation of electronic energies from conditional probability densities
• Conditional probability density functional theory
• A simple and efficient route towards improved energetics within the framework of density-corrected density functional theory
• Using Electronegativity and Hardness to Test Density Functional Universality
• Revisiting Artifacts of Kohn-Sham Density Functionals for Biosimulation