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.

• Publication year

  2015

• Venue

  Journal of Chemical Physics

• Publication date

  2015-04-21

• Fields of study

  Medicine, Physics, Chemistry

• Identifiers
  DOI 10.1063/1.4918710arXiv 1506.05907PMID 25903882
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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