A relativistic study of the electronic and magnetic properties of cerocene and thorocene and its anions

Franklin Ferraro, Cristina Aparecida Barboza, Ramiro Arratia-Pérez

Resultado de la investigación: Article

17 Citas (Scopus)

Resumen

In this study, we evaluated the importance of the relativistic effects on the optical and magnetic properties of cerocene and thorocene and its corresponding anions. The optimized molecular structures show D 8h symmetry for all systems, in good agreement with the experimental data. Atomic charges were analyzed using different approaches (Mulliken, AIM, multipole, and NBO), and the results suggest that the net charge on the thorium is greater than on the cerium atom; however, none of the methodologies were able to predict the expected net charge Ce(III) and Th(IV) atoms. However, by an energy decomposition analysis, a significant electrostatic, ionic, interaction, ∼58% and ∼61%, was found between the metal and the COT 2- rings, respectively. The calculated electronic excitations are underestimated in comparison with the experimental data, while the calculated EPR g-tensors are in agreement with previous theoretical and experimental data. Besides, the NICS analysis shows an increased ring electron delocalization due to the lanthanide and actinide metals.

Idioma originalEnglish
Páginas (desde-hasta)4170-4175
Número de páginas6
PublicaciónJournal of Physical Chemistry A
Volumen116
N.º16
DOI
EstadoPublished - 26 abr 2012

Huella dactilar

Electronic properties
Anions
Magnetic properties
Actinoid Series Elements
Thorium
magnetic properties
anions
Cerium
Lanthanoid Series Elements
Atoms
rings
thorium
relativistic effects
cerium
electronics
metals
Molecular structure
multipoles
Tensors
Paramagnetic resonance

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

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abstract = "In this study, we evaluated the importance of the relativistic effects on the optical and magnetic properties of cerocene and thorocene and its corresponding anions. The optimized molecular structures show D 8h symmetry for all systems, in good agreement with the experimental data. Atomic charges were analyzed using different approaches (Mulliken, AIM, multipole, and NBO), and the results suggest that the net charge on the thorium is greater than on the cerium atom; however, none of the methodologies were able to predict the expected net charge Ce(III) and Th(IV) atoms. However, by an energy decomposition analysis, a significant electrostatic, ionic, interaction, ∼58{\%} and ∼61{\%}, was found between the metal and the COT 2- rings, respectively. The calculated electronic excitations are underestimated in comparison with the experimental data, while the calculated EPR g-tensors are in agreement with previous theoretical and experimental data. Besides, the NICS analysis shows an increased ring electron delocalization due to the lanthanide and actinide metals.",
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A relativistic study of the electronic and magnetic properties of cerocene and thorocene and its anions. / Ferraro, Franklin; Barboza, Cristina Aparecida; Arratia-Pérez, Ramiro.

En: Journal of Physical Chemistry A, Vol. 116, N.º 16, 26.04.2012, p. 4170-4175.

Resultado de la investigación: Article

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