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Title: Orbital-dependent second-order scaled-opposite-spin correlation functionals in the optimized effective potential method

The performance of correlated optimized effective potential (OEP) functionals based on the spin-resolved second-order correlation energy is analysed. The relative importance of singly- and doubly- excited contributions as well as the effect of scaling the same- and opposite- spin components is investigated in detail comparing OEP results with Kohn–Sham (KS) quantities determined via an inversion procedure using accurate ab initio electronic densities. Special attention is dedicated in particular to the recently proposed scaled-opposite–spin OEP functional [I. Grabowski, E. Fabiano, and F. Della Sala, Phys. Rev. B 87, 075103 (2013)] which is the most advantageous from a computational point of view. We find that for high accuracy, a careful, system dependent, selection of the scaling coefficient is required. We analyse several size-extensive approaches for this selection. Finally, we find that a composite approach, named OEP2-SOSh, based on a post-SCF rescaling of the correlation energy can yield high accuracy for many properties, being comparable with the most accurate OEP procedures previously reported in the literature but at substantially reduced computational effort.
Authors:
; ;  [1] ;  [2] ;  [3] ;  [4] ;  [2] ;  [5]
  1. Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, Grudziadzka 5, 87-100 Torun (Poland)
  2. National Nanotechnology Laboratory, Istituto Nanoscienze–CNR, Via per Arnesano, I-73100 Lecce (Italy)
  3. School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)
  4. (Norway)
  5. (IIT), Via Barsanti, 73010 Arnesano (LE) (Italy)
Publication Date:
OSTI Identifier:
22308574
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 2; Other Information: (c) 2014 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; ACCURACY; ELECTRON DENSITY; SPIN