J. Phys. B: At. Mol. Opt. Phys. 33 (28 November 2000) 5139-5149

Accuracy of RCC-SD and PT2/CI methods in all-electron and RECP calculations on Pb and Pb2+

T A Isaev1, N S Mosyagin1, M G Kozlov1, A V Titov1, E Eliav2 and U Kaldor2
1 Petersburg Nuclear Physics Institute, Gatchina, St Petersburg district 188350, Russia
2 School of Chemistry, Tel Aviv University, Tel Aviv 69978, Israel

 Transition energy calculations for low-lying states of Pb and Pb2+ by the four-component versions of the Fock-space RCC-SD and PT2/CI methods are reported. Contributions of valence and core electron correlation are studied in all-electron calculations with the Dirac-Coulomb Hamiltonian. The accuracy of our generalized RECP and the RECP of Christiansen and co-workers is tested. The consideration of only one- and two-body amplitudes for valence electrons in the RCC method for Pb is shown not to be sufficient to reproduce valence excitations within 100-300 cm-1. Correcting RCC-SD results by estimated contributions of triple and quadruple excitations yields an accuracy of about 200 cm-1.

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