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Title: Robust validation of approximate 1-matrix functionals with few-electron harmonium atoms

A simple comparison between the exact and approximate correlation components U of the electron-electron repulsion energy of several states of few-electron harmonium atoms with varying confinement strengths provides a stringent validation tool for 1-matrix functionals. The robustness of this tool is clearly demonstrated in a survey of 14 known functionals, which reveals their substandard performance within different electron correlation regimes. Unlike spot-testing that employs dissociation curves of diatomic molecules or more extensive benchmarking against experimental atomization energies of molecules comprising some standard set, the present approach not only uncovers the flaws and patent failures of the functionals but, even more importantly, also allows for pinpointing their root causes. Since the approximate values of U are computed at exact 1-densities, the testing requires minimal programming and thus is particularly suitable for rapid screening of new functionals.
Authors:
 [1] ; ;  [2] ;  [3]
  1. Institute of Physics, University of Szczecin, Wielkopolska 15, 70-451 Szczecin (Poland)
  2. Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), and Donostia International Physics Center (DIPC), 20018 Donostia, Euskadi (Spain)
  3. (Spain)
Publication Date:
OSTI Identifier:
22493283
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMIZATION; ATOMS; BENCHMARKS; COMPARATIVE EVALUATIONS; DENSITY; DIAGRAMS; DISSOCIATION; ELECTRON CORRELATION; ELECTRONS; FUNCTIONALS; MATRICES; MOLECULES; VALIDATION