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

Journal Article · Sat Mar 07 00:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4913569· OSTI ID:22416211

Choi, Sunghwan; Hong, Kwangwoo; Kim, Jaewook

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 scaling factor regardless of systems.

• OSTI ID: 22416211
• Journal Information: Journal of Chemical Physics, Vol. 142, Issue 9; 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

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