An a b i n i t i o study of low-lying 5f→5f excitations in PuF6

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Abstract
The excited electronic states of PuF6 below 3 eV arise from 5f→5f transitions. These states have been investigated using ab initio wave functions based on a relativistic effective core potential (RECP) for plutonium and nonrelativistic ECP for the fluorines and double‐zeta quality basis sets. The effects of electron correlation were included by configuration interaction, and the effects of spin‐orbit coupling were included by diagonalizing the correlated wave function over an effective spin‐orbit operator. The only previous calculations on PuF6 that include both the effects of configuration interaction (CI) and of spin‐orbit (SO) coupling are the semiempirical ligand field calculations of Kugel et al. The agreement between the present work and that of Kugel et al. is truly remarkable, with the average difference in excitation energies being less than 0.03 eV for the nine lowest transitions. Both sets of results are in general agreement with recent gas‐phase and matrix spectroscopic studies of PuF6.

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