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Title: Communication: Near-locality of exchange and correlation density functionals for 1- and 2-electron systems

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4950845· OSTI ID:1471104
 [1];  [2];  [3];  [3]
  1. Temple Univ., Philadelphia, PA (United States). Dept. of Physics
  2. Temple Univ., Philadelphia, PA (United States). Dept. of Physics, and Dept. of Chemistry
  3. Temple Univ., Philadelphia, PA (United States). Dept. of Physics
+ Show Author Affiliations

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. Here, we show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin density approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.

Research Organization:
Temple Univ., Philadelphia, PA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for the Computational Design of Functional Layered Materials (CCDM)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0012575; DMR-1305135
OSTI ID:
1471104
Alternate ID(s):
OSTI ID: 1253395
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 19; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

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Cited By (8)

Limitations of Global Hybrids in Predicting the Geometries and Torsional Energy Barriers of Dimeric Systems and the Role of Hartree Fock and DFT Exchange journal August 2019
Perspective: Kohn-Sham density functional theory descending a staircase journal October 2016
Exchange functionals based on finite uniform electron gases journal March 2017
A local tensor that unifies kinetic energy density and vorticity in density functional theory journal October 2018
Stretched or noded orbital densities and self-interaction correction in density functional theory journal May 2019
Relevance of the Pauli kinetic energy density for semilocal functionals journal October 2019
Local density approximations from finite systems journal November 2016
Exchange functionals based on finite uniform electron gases text January 2016

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY