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Title: Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

We consider several spin-unrestricted random-phase approximation (RPA) variants for calculating correlation energies, with and without range separation, and test them on datasets of atomization energies and reaction barrier heights. We show that range separation greatly improves the accuracy of all RPA variants for these properties. Moreover, we show that a RPA variant with exchange, hereafter referred to as RPAx-SO2, first proposed by Szabo and Ostlund [J. Chem. Phys. 67, 4351 (1977)] in a spin-restricted closed-shell formalism, and extended here to a spin-unrestricted formalism, provides on average the most accurate range-separated RPA variant for atomization energies and reaction barrier heights. Since this range-separated RPAx-SO2 method had already been shown to be among the most accurate range-separated RPA variants for weak intermolecular interactions [J. Toulouse et al., J. Chem. Phys. 135, 084119 (2011)], this works confirms range-separated RPAx-SO2 as a promising method for general chemical applications.
Authors:
 [1] ;  [2] ;  [2] ; ;  [3] ;  [2] ;  [4] ;  [2]
  1. Sorbonne Universités, UPMC Univ Paris 06, Institut du Calcul et de la Simulation, F-75005 Paris (France)
  2. (France)
  3. Sorbonne Universités, UPMC Univ Paris 06, UMR 7616, Laboratoire de Chimie Théorique, F-75005 Paris (France)
  4. CRM2, Institut Jean Barriol, Université de Lorraine, F-54506 Vandoeuvre-lés-Nancy (France)
Publication Date:
OSTI Identifier:
22415668
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 15; 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; ACCURACY; ATOMIZATION; BENCHMARKS; CHEMICAL REACTIONS; DATASETS; ELECTRON CORRELATION; INTERMOLECULAR FORCES; RANDOM PHASE APPROXIMATION; SPIN