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Title: Basis convergence of range-separated density-functional theory

Range-separated density-functional theory (DFT) is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N{sub 2}, and H{sub 2}O) with cardinal number X of the Dunning basis sets cc − p(C)V XZ and find that the error in the correlation energy is best fitted by an exponential inmore » X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.« less
Authors:
;  [1] ;  [2] ;  [2] ; ;  [1] ;  [2]
  1. Sorbonne Universités, UPMC Univ Paris 06, UMR 7616, Laboratoire de Chimie Théorique, F-75005 Paris (France)
  2. (France)
Publication Date:
OSTI Identifier:
22416139
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 7; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ANGULAR MOMENTUM; APPROXIMATIONS; COALESCENCE; COMPARATIVE EVALUATIONS; CONVERGENCE; DENSITY FUNCTIONAL METHOD; ELECTRON CORRELATION; ELECTRON-ELECTRON COUPLING; ELECTRONS; EXTRAPOLATION; HELIUM; MANY-BODY PROBLEM; NEON; PARTIAL WAVES; POLYNOMIALS; WATER; WAVE FUNCTIONS