Electronic structure and molecular properties of the heptacyanorhenate [Re(CN)7]3- and [Re(CN)7]4- complexes

Jorge David, Fernando Mendizábal, Ramiro Arratia-Pérez

Resultado de la investigación: Article

6 Citas (Scopus)

Resumen

We report scalar relativistic and Dirac scattered wave (DSW) calculations on the heptacyanorhenate [Re(CN)7]3- and Re(CN) 7 4- complexes. Both the ground and lowest excited states of each complex split by spin-orbit interaction by about 0.3 eV. The calculated molecular electronegativities χ indicate that the open-shell complex is less reactive than the closed-shell complex, in agreement with experimental observations. The calculations indicate that the ground state spin density is highly anisotropic and that spin-orbit effects are responsible for the magnetic anisotropy of the molecular g tensor of the Re(CN)7 3- complex. The calculated optical electronic transitions for both complexes with a polarizable continuum model using a time-dependent density functional (TDDFT)/B3LYP formalism are in reasonable agreement with those observed in the absorption spectrum.

Idioma originalEnglish
Páginas (desde-hasta)1072-1077
Número de páginas6
PublicaciónJournal of Physical Chemistry A
Volumen110
N.º3
DOI
EstadoPublished - 26 feb 2006

Huella dactilar

molecular properties
Electronic structure
Orbits
electronic structure
Electronegativity
Magnetic anisotropy
spin-orbit interactions
Excited states
Ground state
Tensors
Absorption spectra
tensors
scalars
formalism
continuums
orbits
absorption spectra
anisotropy
ground state
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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abstract = "We report scalar relativistic and Dirac scattered wave (DSW) calculations on the heptacyanorhenate [Re(CN)7]3- and Re(CN) 7 4- complexes. Both the ground and lowest excited states of each complex split by spin-orbit interaction by about 0.3 eV. The calculated molecular electronegativities χ indicate that the open-shell complex is less reactive than the closed-shell complex, in agreement with experimental observations. The calculations indicate that the ground state spin density is highly anisotropic and that spin-orbit effects are responsible for the magnetic anisotropy of the molecular g tensor of the Re(CN)7 3- complex. The calculated optical electronic transitions for both complexes with a polarizable continuum model using a time-dependent density functional (TDDFT)/B3LYP formalism are in reasonable agreement with those observed in the absorption spectrum.",
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Electronic structure and molecular properties of the heptacyanorhenate [Re(CN)7]3- and [Re(CN)7]4- complexes. / David, Jorge; Mendizábal, Fernando; Arratia-Pérez, Ramiro.

En: Journal of Physical Chemistry A, Vol. 110, N.º 3, 26.02.2006, p. 1072-1077.

Resultado de la investigación: Article

TY - JOUR

T1 - Electronic structure and molecular properties of the heptacyanorhenate [Re(CN)7]3- and [Re(CN)7]4- complexes

AU - David, Jorge

AU - Mendizábal, Fernando

AU - Arratia-Pérez, Ramiro

PY - 2006/2/26

Y1 - 2006/2/26

N2 - We report scalar relativistic and Dirac scattered wave (DSW) calculations on the heptacyanorhenate [Re(CN)7]3- and Re(CN) 7 4- complexes. Both the ground and lowest excited states of each complex split by spin-orbit interaction by about 0.3 eV. The calculated molecular electronegativities χ indicate that the open-shell complex is less reactive than the closed-shell complex, in agreement with experimental observations. The calculations indicate that the ground state spin density is highly anisotropic and that spin-orbit effects are responsible for the magnetic anisotropy of the molecular g tensor of the Re(CN)7 3- complex. The calculated optical electronic transitions for both complexes with a polarizable continuum model using a time-dependent density functional (TDDFT)/B3LYP formalism are in reasonable agreement with those observed in the absorption spectrum.

AB - We report scalar relativistic and Dirac scattered wave (DSW) calculations on the heptacyanorhenate [Re(CN)7]3- and Re(CN) 7 4- complexes. Both the ground and lowest excited states of each complex split by spin-orbit interaction by about 0.3 eV. The calculated molecular electronegativities χ indicate that the open-shell complex is less reactive than the closed-shell complex, in agreement with experimental observations. The calculations indicate that the ground state spin density is highly anisotropic and that spin-orbit effects are responsible for the magnetic anisotropy of the molecular g tensor of the Re(CN)7 3- complex. The calculated optical electronic transitions for both complexes with a polarizable continuum model using a time-dependent density functional (TDDFT)/B3LYP formalism are in reasonable agreement with those observed in the absorption spectrum.

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