Energy density functionals from the strongcoupling limit applied to the anions of the He isoelectronic series
Abstract
Anions and radicals are important for many applications including environmental chemistry, semiconductors, and charge transfer, but are poorly described by the available approximate energy density functionals. Here we test an approximate exchangecorrelation functional based on the exact strongcoupling limit of the HohenbergKohn functional on the prototypical case of the He isoelectronic series with varying nuclear charge Z < 2, which includes weakly bound negative ions and a quantum phase transition at a critical value of Z, representing a big challenge for density functional theory. We use accurate wavefunction calculations to validate our results, comparing energies and KohnSham potentials, thus also providing useful reference data close to and at the quantum phase transition. We show that our functional is able to bind H{sup −} and to capture in general the physics of loosely bound anions, with a tendency to strongly overbind that can be proven mathematically. We also include corrections based on the uniform electron gas which improve the results.
 Authors:

 Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, FEW, Vrije Universiteit, De Boelelaan 1083, 1081HV Amsterdam (Netherlands)
 Laboratory of Atomic and Solid State Physics, Cornell University, Ithaca, New York 14853 (United States)
 Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716 (United States)
 Publication Date:
 OSTI Identifier:
 22253116
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 140; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 00219606
 Country of Publication:
 United States
 Language:
 English
 Subject:
 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANIONS; APPROXIMATIONS; DENSITY FUNCTIONAL METHOD; ELECTRON GAS; ENERGY DENSITY; FUNCTIONALS; PHASE TRANSFORMATIONS; STRONGCOUPLING MODEL; WAVE FUNCTIONS
Citation Formats
Mirtschink, André, GoriGiorgi, Paola, Umrigar, C. J., and Morgan, John D. Energy density functionals from the strongcoupling limit applied to the anions of the He isoelectronic series. United States: N. p., 2014.
Web. doi:10.1063/1.4871018.
Mirtschink, André, GoriGiorgi, Paola, Umrigar, C. J., & Morgan, John D. Energy density functionals from the strongcoupling limit applied to the anions of the He isoelectronic series. United States. doi:10.1063/1.4871018.
Mirtschink, André, GoriGiorgi, Paola, Umrigar, C. J., and Morgan, John D. Wed .
"Energy density functionals from the strongcoupling limit applied to the anions of the He isoelectronic series". United States. doi:10.1063/1.4871018.
@article{osti_22253116,
title = {Energy density functionals from the strongcoupling limit applied to the anions of the He isoelectronic series},
author = {Mirtschink, André and GoriGiorgi, Paola and Umrigar, C. J. and Morgan, John D.},
abstractNote = {Anions and radicals are important for many applications including environmental chemistry, semiconductors, and charge transfer, but are poorly described by the available approximate energy density functionals. Here we test an approximate exchangecorrelation functional based on the exact strongcoupling limit of the HohenbergKohn functional on the prototypical case of the He isoelectronic series with varying nuclear charge Z < 2, which includes weakly bound negative ions and a quantum phase transition at a critical value of Z, representing a big challenge for density functional theory. We use accurate wavefunction calculations to validate our results, comparing energies and KohnSham potentials, thus also providing useful reference data close to and at the quantum phase transition. We show that our functional is able to bind H{sup −} and to capture in general the physics of loosely bound anions, with a tendency to strongly overbind that can be proven mathematically. We also include corrections based on the uniform electron gas which improve the results.},
doi = {10.1063/1.4871018},
journal = {Journal of Chemical Physics},
issn = {00219606},
number = 18,
volume = 140,
place = {United States},
year = {2014},
month = {5}
}