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Systematic Gaussian basis‐set limit using completeness‐optimized primitive sets. A case for magnetic properties
Author(s) -
Manninen Pekka,
Vaara Juha
Publication year - 2006
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.20358
Subject(s) - completeness (order theory) , exponent , gaussian , basis (linear algebra) , mathematics , statistical physics , basis set , basis function , quantum mechanics , mathematical analysis , physics , geometry , philosophy , linguistics , molecule
We discuss the connection between the completeness of a basis set, measured by the completeness profiles introduced by Chong (Can J Chem 1995, 73, 79) at a certain exponent interval, and the possibility of reproducing molecular properties that arise either in the region close to the atomic nuclei or in the valence region. We present a scheme for generating completeness‐optimized Gaussian basis sets, in which a preselected range of exponents is covered to an arbitrary accuracy. This is done by requiring Gaussian functions, the exponents of which are selected without reference to the atomic structure, to span the range with completeness profile as close to unity as wanted with as few functions as possible. The initial exponent range can be chosen suitable for calculations of molecular energetics or other valence‐like properties. By extending the exponent range, properties requiring augmentation of the basis at a given angular momentum value and/or in a given distance range from the nucleus may be straightforwardly and systematically treated. In this scheme a universal, element‐independent exponent set is generated in an automated way. The relation of basis‐set completeness and performance in the calculation of magnetizability, nuclear magnetic shielding, and spin–spin coupling is tested with the completeness‐optimized primitive sets and literature basis sets. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 434–445, 2006