Bonding nature and electron delocalization of An(COT)2, An = Th, Pa, U

Resultado de la investigación: Article

21 Citas (Scopus)

Resumen

A systematic study of a series of An(COT)2 compounds, where An = Th, Pa, U, and COT represents cyclooctatetraene, has been performed using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects, taking into account all of the electrons for the optimization and explicitly including spin-orbit coupling effects. Time-dependent density functional theory (TDDFT) was used to calculate the excitation energies with the GGA SAOP functional, and the electronic transitions were analyzed using double group irreducible representations. The calculated excitation energies are in perfect correlation with the increment of the ring delocalization as it increases along the actinide series. These results are sufficient to ensure that, for these complexes, the increment in delocalization, as indicated by ELF bifurcation and NICS analysis, leads to a shift in the maximum wavelength of absorption in the visible region. Also, delocalization in the COT ring increases along the actinide series, so the systems become more aromatic because of a modulation induced by the actinides.

Idioma originalEnglish
Páginas (desde-hasta)8997-9003
Número de páginas7
PublicaciónJournal of Physical Chemistry A
Volumen115
N.º32
DOI
EstadoPublished - 18 ago 2011

Huella dactilar

actinide series
Actinoid Series Elements
Excitation energy
density functional theory
Density functional theory
Electrons
rings
relativistic effects
excitation
Hamiltonians
electrons
inclusions
orbits
modulation
optimization
energy
shift
Orbits
electronics
Modulation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

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title = "Bonding nature and electron delocalization of An(COT)2, An = Th, Pa, U",
abstract = "A systematic study of a series of An(COT)2 compounds, where An = Th, Pa, U, and COT represents cyclooctatetraene, has been performed using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects, taking into account all of the electrons for the optimization and explicitly including spin-orbit coupling effects. Time-dependent density functional theory (TDDFT) was used to calculate the excitation energies with the GGA SAOP functional, and the electronic transitions were analyzed using double group irreducible representations. The calculated excitation energies are in perfect correlation with the increment of the ring delocalization as it increases along the actinide series. These results are sufficient to ensure that, for these complexes, the increment in delocalization, as indicated by ELF bifurcation and NICS analysis, leads to a shift in the maximum wavelength of absorption in the visible region. Also, delocalization in the COT ring increases along the actinide series, so the systems become more aromatic because of a modulation induced by the actinides.",
author = "Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Murillo-L{\'o}pez, {Juliana A.} and Ramiro Arratia-P{\'e}rez",
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language = "English",
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Bonding nature and electron delocalization of An(COT)2, An = Th, Pa, U. / Páez-Hernández, Dayán; Murillo-López, Juliana A.; Arratia-Pérez, Ramiro.

En: Journal of Physical Chemistry A, Vol. 115, N.º 32, 18.08.2011, p. 8997-9003.

Resultado de la investigación: Article

TY - JOUR

T1 - Bonding nature and electron delocalization of An(COT)2, An = Th, Pa, U

AU - Páez-Hernández, Dayán

AU - Murillo-López, Juliana A.

AU - Arratia-Pérez, Ramiro

PY - 2011/8/18

Y1 - 2011/8/18

N2 - A systematic study of a series of An(COT)2 compounds, where An = Th, Pa, U, and COT represents cyclooctatetraene, has been performed using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects, taking into account all of the electrons for the optimization and explicitly including spin-orbit coupling effects. Time-dependent density functional theory (TDDFT) was used to calculate the excitation energies with the GGA SAOP functional, and the electronic transitions were analyzed using double group irreducible representations. The calculated excitation energies are in perfect correlation with the increment of the ring delocalization as it increases along the actinide series. These results are sufficient to ensure that, for these complexes, the increment in delocalization, as indicated by ELF bifurcation and NICS analysis, leads to a shift in the maximum wavelength of absorption in the visible region. Also, delocalization in the COT ring increases along the actinide series, so the systems become more aromatic because of a modulation induced by the actinides.

AB - A systematic study of a series of An(COT)2 compounds, where An = Th, Pa, U, and COT represents cyclooctatetraene, has been performed using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects, taking into account all of the electrons for the optimization and explicitly including spin-orbit coupling effects. Time-dependent density functional theory (TDDFT) was used to calculate the excitation energies with the GGA SAOP functional, and the electronic transitions were analyzed using double group irreducible representations. The calculated excitation energies are in perfect correlation with the increment of the ring delocalization as it increases along the actinide series. These results are sufficient to ensure that, for these complexes, the increment in delocalization, as indicated by ELF bifurcation and NICS analysis, leads to a shift in the maximum wavelength of absorption in the visible region. Also, delocalization in the COT ring increases along the actinide series, so the systems become more aromatic because of a modulation induced by the actinides.

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