Minimally augmented Karlsruhe basis sets

• Published in: Theoretical chemistry accounts Vol. 128; no. 3; pp. 295 - 305
• Main Authors: Zheng, Jingjing, Xu, Xuefei, Truhlar, Donald G.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer-Verlag 01.02.2011
• Subjects: Atomic/Molecular Structure and Spectra; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Organic Chemistry; Physical Chemistry; Regular Article; Theoretical and Computational Chemistry; Double zeta; Electron affinities; Diffuse functions; Barrier heights; Triple zeta; Quadruple zeta; Electronic structure; Minimally augmented basis set; DBH24/08 database; ma-TZVP; Ionization potentials; Density functional theory; Bond dissociation energies; S22A database; Basis sets; Noncovalent interactions
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-010-0846-z

We propose an extension of the basis sets proposed by Ahlrichs and coworkers at Karlsruhe (these basis sets are designated as the second-generation default or “def2” basis sets in the Turbomole program). The Karlsruhe basis sets are very appealing because they constitute balanced and economical basis sets of graded quality from partially polarized double zeta to heavily polarized quadruple zeta for all elements up to radon ( Z  = 86). The extension consists of adding a minimal set of diffuse functions to a subset of the elements. This yields basis sets labeled minimally augmented or with “ma” as a prefix. We find that diffuse functions are not quite as important for the def2 basis sets as they are for Pople basis sets, but they are still necessary for good results on barrier heights and electron affinities. We provide assessments and validations of this extension for a variety of data sets and representative cases. We recommend the new ma-TZVP basis set for general-purpose applications of density functional theory.