Large-scale relativistic correlation calculations: Levels ofPr+3

A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species

“…To quote one example, the average error for the f 2 levels of Pr 3+ was 222 cm −1 , four times smaller than that of an extensive multiconfigurational Dirac-Fock calculation. 25 The quality of results was sufficient to allow reliable predictions for the nature of the ground states and spectra of a number of superheavy elements. Molecules calculated by the method include AuH, 35 Au 2 , 36 HgH, 37 and TlF.…”

“…The FSCC method has been applied to a large number of atoms and molecules, including transition and heavy elements, with experimentally known spectroscopic properties. Examples are atomic gold, 24,25 Fr, 26 the lanthanides La, 27 Pr, 28 Yb, and Lu, 29 the actinides Ac, 30 Th, 31 and U, 28 as well as Hg, 31 Tl, 30,32 Pb, 33 and Bi. 34 Good agreement with experimental transition energies ͑within a few hundreds of wave numbers͒ was obtained.…”

Nephelauxetic effect and 〈r〉4f radial integrals of Pr3+ in crystals

“…Later, Morrison and Rajnak [9] have calculated the effective two-body operators of even rank for Pr 3+ which reduce the Slater integrals compared to their Hartree-Fock values. Cai et al [10] have applied relativistic correlation method to obtain the energy levels of the same ion in good agreement with the experiment, including the 1 S o level. Using relativistic coupled-cluster (RCC) technique and extensive basis sets, Eliav et al [11] have computed the ionization potentials, the energy levels and the fine structure splittings for Pr 3+ with reasonable accuracy.…”

Study of Actinides by Relativistic Coupled Cluster Methods

“…Excellent agreement with experiment was obtained, with an MAE of 222 cm −1 for the Pr 3+ levels and 114 cm −1 for U 4+ . The error for Pr 3+ was four times smaller than that of the MCDF calculation [87], demonstrating the more comprehensive inclusion of dynamic correlation by CC. More recently, a larger basis set was employed, extending the analysis to include the excited states of U 5+ and the 5f 2 , 5f 7s, and 5f 6d states of U 4+ , which are important in interpreting the electronic spectrum of the neutral UO 2 molecule [25].…”