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Title: Accuracy of Lagrange-sinc functions as a basis set for electronic structure calculations of atoms and molecules

We developed a self-consistent field program based on Kohn-Sham density functional theory using Lagrange-sinc functions as a basis set and examined its numerical accuracy for atoms and molecules through comparison with the results of Gaussian basis sets. The result of the Kohn-Sham inversion formula from the Lagrange-sinc basis set manifests that the pseudopotential method is essential for cost-effective calculations. The Lagrange-sinc basis set shows faster convergence of the kinetic and correlation energies of benzene as its size increases than the finite difference method does, though both share the same uniform grid. Using a scaling factor smaller than or equal to 0.226 bohr and pseudopotentials with nonlinear core correction, its accuracy for the atomization energies of the G2-1 set is comparable to all-electron complete basis set limits (mean absolute deviation ≤1 kcal/mol). The same basis set also shows small mean absolute deviations in the ionization energies, electron affinities, and static polarizabilities of atoms in the G2-1 set. In particular, the Lagrange-sinc basis set shows high accuracy with rapid convergence in describing density or orbital changes by an external electric field. Moreover, the Lagrange-sinc basis set can readily improve its accuracy toward a complete basis set limit by simply decreasing the scalingmore » factor regardless of systems.« less
Authors:
; ; ;  [1]
  1. Department of Chemistry, KAIST, 291 Daehak-ro, Yuseong-gu, Daejeon 305-701 (Korea, Republic of)
Publication Date:
OSTI Identifier:
22416211
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 9; 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; AFFINITY; ATOMS; BENZENE; COMPARATIVE EVALUATIONS; CONVERGENCE; CORRECTIONS; DENSITY; DENSITY FUNCTIONAL METHOD; ELECTRIC FIELDS; ELECTRON CORRELATION; ELECTRONIC STRUCTURE; ELECTRONS; FINITE DIFFERENCE METHOD; MOLECULES; NONLINEAR PROBLEMS; POLARIZABILITY; POTENTIALS; SELF-CONSISTENT FIELD