Basis convergence of range-separated density-functional theory

Journal Article · Sat Feb 21 00:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4907920· OSTI ID:22416139

Franck, Odile; Mussard, Bastien ^[1]; Luppi, Eleonora; Toulouse, Julien ^[1]

---

1. Sorbonne Universités, UPMC Univ Paris 06, UMR 7616, Laboratoire de Chimie Théorique, F-75005 Paris (France)

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 in 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.

• OSTI ID: 22416139
• Journal Information: Journal of Chemical Physics, Vol. 142, Issue 7; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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