Theoretical study of the structure and bonding in ThC 2 and UC 2

Peter Pogány, Attila Kovács, Zoltán Varga, F. Matthias Bickelhaupt, Rudy J.M. Konings

Research output: Contribution to journalArticle

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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.

Original languageEnglish (US)
Pages (from-to)747-755
Number of pages9
JournalJournal of Physical Chemistry A
Volume116
Issue number1
DOIs
StatePublished - Jan 12 2012

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Electronic states
Electronic structure
Geometry
geometry
Actinoid Series Elements
electronic structure
molecular properties
electronics
Discrete Fourier transforms
determinants
Ground state
ground state
energy
probes

Cite this

Pogány, P., Kovács, A., Varga, Z., Bickelhaupt, F. M., & Konings, R. J. M. (2012). Theoretical study of the structure and bonding in ThC 2 and UC 2 Journal of Physical Chemistry A, 116(1), 747-755. https://doi.org/10.1021/jp210190m

Theoretical study of the structure and bonding in ThC 2 and UC 2 . / Pogány, Peter; Kovács, Attila; Varga, Zoltán; Bickelhaupt, F. Matthias; Konings, Rudy J.M.

In: Journal of Physical Chemistry A, Vol. 116, No. 1, 12.01.2012, p. 747-755.

Research output: Contribution to journalArticle

Pogány, P, Kovács, A, Varga, Z, Bickelhaupt, FM & Konings, RJM 2012, 'Theoretical study of the structure and bonding in ThC 2 and UC 2 ', Journal of Physical Chemistry A, vol. 116, no. 1, pp. 747-755. https://doi.org/10.1021/jp210190m
Pogány P, Kovács A, Varga Z, Bickelhaupt FM, Konings RJM. Theoretical study of the structure and bonding in ThC 2 and UC 2 Journal of Physical Chemistry A. 2012 Jan 12;116(1):747-755. https://doi.org/10.1021/jp210190m
Pogány, Peter ; Kovács, Attila ; Varga, Zoltán ; Bickelhaupt, F. Matthias ; Konings, Rudy J.M. / Theoretical study of the structure and bonding in ThC 2 and UC 2 In: Journal of Physical Chemistry A. 2012 ; Vol. 116, No. 1. pp. 747-755.
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