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Theoretical study of the structure and bonding in ThC2 and UC2.

Authors
  • Pogány, Peter
  • Kovács, Attila
  • Varga, Zoltán
  • Bickelhaupt, F Matthias
  • Konings, Rudy J M
Type
Published Article
Journal
The Journal of Physical Chemistry A
Publisher
American Chemical Society
Publication Date
Jan 12, 2012
Volume
116
Issue
1
Pages
747–755
Identifiers
DOI: 10.1021/jp210190m
PMID: 22191481
Source
Medline
License
Unknown

Abstract

The electronic structure and various molecular properties of the actinide (An) dicarbides ThC(2) and UC(2) were investigated by relativistic quantum chemical calculations. We probe five possible geometrical arrangements: two triangular structures including an acetylide (C(2)) moiety, as well as the linear AnCC, CAnC, and bent CAnC geometries. Our calculations at various levels of theory indicate that the triangular species are energetically more favorable, while the latter three arrangements proved to be higher-energy structures. Our SO-CASPT2 calculations give the ground-state molecular geometry for both ThC(2) and UC(2) as the symmetric (C(2v)) triangular structure. The similar and, also very close in energy, asymmetric (C(s)) triangular geometry belongs to a different electronic state. DFT and single-determinant ab initio methods failed to distinguish between these two similar electronic states demonstrating the power of multiconfiguration ab initio methods to deal with such subtle and delicate problems. We report detailed data on the electronic structure and bonding properties of the most relevant structures.

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