Structure and other molecular properties of actinide trichlorides AnCl 3 (An = Th-Cm)

Attila Kovács, Rudy J.M. Konings, Zoltan Varga, Dénes Szieberth

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The ground-state molecular properties of the trichlorides of light actinides (An = Th-Cm) have been predicted by state-of-the-art quantum chemical calculations. The ground electronic states have been determined by multireference calculations at the CASPT2 level including both scalar and spin-orbit relativistic effects. These studies supported the expected single-configuration character of ThCl3 and CmCl3 with their well-defined 6dσ/7s hybrid and 5f7 configurations, respectively. In contrast, the intermediate actinides (PaCl3- AmCl3) with partly filled 5f shells have numerous very low-lying excited states and consequently a mixed character of the spin-orbit ground states. Apart from the planar ThCl3 the ground-state molecular geometries proved to be pyramidal with C3v symmetry. The gradually decreasing An-Cl bond distances reveal the actinide contraction known for the atomic and ionic radii of these actinide atoms. Other ground-state molecular properties as vibrational frequencies and natural charges have been obtained by density functional theory calculations using the B3LYP exchange-correlation functional in conjunction with small-core relativistic energy-consistent pseudopotentials for the actinides.

Original languageEnglish (US)
Pages (from-to)11357-11363
Number of pages7
JournalJournal of Physical Chemistry A
Issue number44
StatePublished - Nov 7 2013

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