Abstract.
Fully relativistic, four-component Dirac–Fock calculations and quasirelativistic pseudopotential calculations at different ab initio levels are used to study the bonding trends among the naked, triatomic [OAnO]q+ groups or the oxyfluorides [AnO n F m ]q with f 0 configurations. The triatomic f 0 series is suggested to range from the bent ThO2 via the linear OPaO+ to at least NpO2 3+, a possible new gas-phase species. The neutral oxyfluoride molecules include the experimentally unknown NpO2F3 and PuO2F4. The latter is a candidate for the so far unknown oxidation state Pu(VIII), which is found to lie considerably above Pu(VI), but to be locally stable. Their all-oxygen isoelectronic analogues are NpO5 3−, known in the solid state, and the unknown PuO6 4−. Further possible candidates for Pu(VIII) are PuO4(D 4h ) and the cube-shaped PuF8(O h ). Isoelectronic UF8 2− is calculated to be D 4d , in agreement with experiment.
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Received: 18 May 2001 / Accepted: 21 June 2001 / Published online: 11 October 2001
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Straka, M., Dyall, K. & Pyykkö, P. Ab initio study of bonding trends for f0 actinide oxyfluoride species. Theor Chem Acc 106, 393–403 (2001). https://doi.org/10.1007/s002140100295
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DOI: https://doi.org/10.1007/s002140100295