Theoretical Chemistry Accounts

, Volume 117, Issue 4, pp 587–597

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


    • Forschungszentrum KarlsruheInstitute of Nanotechnology
    • Lehrstuhl für Theoretische ChemieRuhr-Universität Bochum
  • Christof Hättig
    • Lehrstuhl für Theoretische ChemieRuhr-Universität Bochum
  • Sebastian Höfener
    • Institut für Physikalische ChemieUniversität Karlsruhe (TH)
  • Wim Klopper
    • Forschungszentrum KarlsruheInstitute of Nanotechnology
    • Institut für Physikalische ChemieUniversität Karlsruhe (TH)
Regular Article

DOI: 10.1007/s00214-007-0250-5

Cite this article as:
Hellweg, A., Hättig, C., Höfener, S. et al. Theor Chem Acc (2007) 117: 587. doi:10.1007/s00214-007-0250-5


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 Møller–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-ζ and quadruple-ζ 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 Møller–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.

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© Springer-Verlag 2007