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On the basis‐set dependence of local and integrated electron density properties: Application of a new computer program for quantum‐chemical density analysis
Author(s) -
Volkov Anatoliy,
Koritsanszky Tibor,
Chodkiewicz Michal,
King Harry F.
Publication year - 2008
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21160
Subject(s) - basis set , basis (linear algebra) , quantum chemical , electron density , set (abstract data type) , electron , computer program , quantum , density functional theory , statistical physics , computer science , computational chemistry , chemistry , physics , quantum mechanics , mathematics , molecule , geometry , operating system , programming language
A new computer program for post‐processing analysis of quantum‐chemical electron densities is described. The code can work with Slater‐ and Gaussian‐type basis functions of arbitrary angular momentum. It has been applied to explore the basis‐set dependence of the electron density and its Laplacian in terms of local and integrated topological properties. Our analysis, including Gaussian/Slater basis sets up to sextuple/quadruple‐zeta order, shows that these properties considerably depend on the choice of type and number of primitives utilized in the wavefunction expansion. Basis sets with high angular momentum ( l = 5 or l = 6) are necessary to achieve convergence for local properties of the density and the Laplacian. In agreement with previous studies, atomic charges defined within Bader's Quantum Theory of Atoms in Molecules appear to be much more basis‐set dependent than the Hirshfeld's stockholder charges. The former ones converge only at the quadruple‐zeta/higher level with Gaussian/Slater functions. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009