Theoretical Chemistry Accounts

, Volume 100, Issue 1, pp 103–111

Core-valence correlation effects for molecules containing first-row atoms. Accurate results using effective core polarization potentials

  • Andreas Nicklass
  • Kirk A. Peterson
Regular article

DOI: 10.1007/s002140050370

Cite this article as:
Nicklass, A. & Peterson, K. Theor Chem Acc (1998) 100: 103. doi:10.1007/s002140050370


The accuracy of employing effective core polarization potentials (CPPs) to account for the effects of core-valence correlation on the spectroscopic constants and dissociation energies of the molecules B2, C2, N2, O2, F2, CO, CN, CH, HF, and C2H2 has been investigated by comparison to accurate all-electron benchmark calculations. The results obtained from the calculations employing CPPs were surprisingly accurate in every case studied, reducing the errors in the calculated valence De values from a maximum of nearly 2.5 kcal/mol to just 0.3 kcal/mol. The effects of enlarging the basis set and using higher-order valence electron correlation treatments were found to have only a small influence on the core-valence correlation effect predicted by the CPPs. Thus, to accurately recover the effects of intershell correlation, effective core polarization potentials such as the ones used in the present work provide an attractive alternative to carrying out computationally demanding calculations where the core electrons are explicitly included in the correlation treatment.

Key words: Core-valence correlation Core polarization potentials 

Copyright information

© Springer-Verlag Berlin Heidelberg 1998

Authors and Affiliations

  • Andreas Nicklass
    • 1
  • Kirk A. Peterson
    • 1
  1. 1.Department of Chemistry, Washington State University and the Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352, USAUS

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