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

Attila Kovács, Rudy J M Konings, Z. Varga, D. Szieberth

Research output: Contribution to journalArticle

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Abstract

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
Pages (from-to)11357-11363
Number of pages7
JournalJournal of Physical Chemistry A
Volume117
Issue number44
DOIs
Publication statusPublished - Nov 7 2013

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Actinoid Series Elements
molecular properties
chlorides
Ground state
ground state
orbits
Orbits
relativistic effects
configurations
pseudopotentials
contraction
Electronic states
Vibrational spectra
Excited states
Density functional theory
scalars
density functional theory
radii
symmetry
geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Structure and other molecular properties of actinide trichlorides AnCl 3 (An = Th-Cm). / Kovács, Attila; Konings, Rudy J M; Varga, Z.; Szieberth, D.

In: Journal of Physical Chemistry A, Vol. 117, No. 44, 07.11.2013, p. 11357-11363.

Research output: Contribution to journalArticle

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