Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn

Arnim Hellweg,a,b,* Christof Hättig,b Sebastian Höfener,c Wim Kloppera,c
aInstitut für Nanotechnologie, Forschungszentrum Karlsruhe, D-76344 Karlsruhe, Germany
bLehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany
cLehrstuhl für Theoretische Chemie, Institut für Physikalische Chemie, Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany

Theo. Chem. Acc., 117, 587-597 (2007).
Received: 8 November 2006 / Accepted: 21 December 2006 / Published online: 23 January 2007

The introduction of the resolution-of-the-identity (RI) approximation for electron repulsion integrals in quantum chemical calculations requires in addition to the orbital basis so-called auxiliary or fitting basis sets. We report here such auxiliary basis sets optimized for second-order M phi ller-Plesset perturbation theory for the recently published (Weigend and Ahlrichs Phys Chem Chem Phys, 2005, 7, 3297-3305) segmented contracted Gaussian basis sets of split, triple-zeta and quadruple-zeta valence quality for the atoms Rb-Rn (except lanthanides). These basis sets are designed for use in connection with small-core effective core potentials including scalar relativistic corrections. Hereby accurate resolution-of-the-identity calculations with second-order M phi ller-Plesset perturbation theory (MP2) and related methods can now be performed for molecules containing elements from H to Rn. The error of the RI approximation has been evaluated for a test set of 385 small and medium sized molecules, which represent the common oxidation states of each element, and is compared with the one-electron basis set error, estimated based on highly accurate explicitly correlated MP2-R12 calculations. With the reported auxiliary basis sets the RI error for MP2 correlation energies is typically two orders of magnitude smaller than the one-electron basis set error, independent on the position of the atoms in the periodic table.

*E-mail to: arnim.hellweg@theochem.rub.de

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