Density functional study on Keggin heteropolyanions containing fifth period main group heteroatoms

Francisca Clavería-Cádiz, Ramiro Arratia-Pérez, Desmond MacLeod-Carey

Resultado de la investigación: Article

4 Citas (Scopus)

Resumen

In this article, a serie of density functional theory (DFT) calculations were carried out on Keggin heteropolyanions[XM12O40]n- (X = Sn(IV), Sb(V) and Te(VI); M = Mo and W; n = 2,3,4) to analyze their molecular structure, vibrational spectra and electronic structure. The energy and composition of the frontier orbitals resemble those containing internal heteroatoms of preceding periods. We found that the diameter of the encapsulated internal{XO4}subunit varies as X does, while{M12O36}size and distances remain almost constant along the series. Vibrational modes calculations show that exist a dependency of the frequency and the anionic charge, nature of the heteroatom X and calculation methodology. Energy decomposition analysis of the{XO4}–{M12O36}interaction shows a predominant ionic character due to the high charge of the{XO4}anionic subunit. COSMO solvation model enabled us to compare heteropolyanions with different total charges. Our results suggest the possibility that these Keggin anions should be stable, being a new challenge for synthetic inorganic chemists.

Idioma originalEnglish
Páginas (desde-hasta)478-486
Número de páginas9
PublicaciónPolyhedron
Volumen117
DOI
EstadoPublished - 1 ene 2016

Huella dactilar

Solvation
Vibrational spectra
vibrational spectra
Molecular structure
Electronic structure
Density functional theory
Anions
solvation
vibration mode
molecular structure
Negative ions
methodology
density functional theory
electronic structure
anions
Decomposition
decomposition
orbitals
energy
Chemical analysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Citar esto

Clavería-Cádiz, Francisca ; Arratia-Pérez, Ramiro ; MacLeod-Carey, Desmond. / Density functional study on Keggin heteropolyanions containing fifth period main group heteroatoms. En: Polyhedron. 2016 ; Vol. 117. pp. 478-486.
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Density functional study on Keggin heteropolyanions containing fifth period main group heteroatoms. / Clavería-Cádiz, Francisca; Arratia-Pérez, Ramiro; MacLeod-Carey, Desmond.

En: Polyhedron, Vol. 117, 01.01.2016, p. 478-486.

Resultado de la investigación: Article

TY - JOUR

T1 - Density functional study on Keggin heteropolyanions containing fifth period main group heteroatoms

AU - Clavería-Cádiz, Francisca

AU - Arratia-Pérez, Ramiro

AU - MacLeod-Carey, Desmond

PY - 2016/1/1

Y1 - 2016/1/1

N2 - In this article, a serie of density functional theory (DFT) calculations were carried out on Keggin heteropolyanions[XM12O40]n- (X = Sn(IV), Sb(V) and Te(VI); M = Mo and W; n = 2,3,4) to analyze their molecular structure, vibrational spectra and electronic structure. The energy and composition of the frontier orbitals resemble those containing internal heteroatoms of preceding periods. We found that the diameter of the encapsulated internal{XO4}subunit varies as X does, while{M12O36}size and distances remain almost constant along the series. Vibrational modes calculations show that exist a dependency of the frequency and the anionic charge, nature of the heteroatom X and calculation methodology. Energy decomposition analysis of the{XO4}–{M12O36}interaction shows a predominant ionic character due to the high charge of the{XO4}anionic subunit. COSMO solvation model enabled us to compare heteropolyanions with different total charges. Our results suggest the possibility that these Keggin anions should be stable, being a new challenge for synthetic inorganic chemists.

AB - In this article, a serie of density functional theory (DFT) calculations were carried out on Keggin heteropolyanions[XM12O40]n- (X = Sn(IV), Sb(V) and Te(VI); M = Mo and W; n = 2,3,4) to analyze their molecular structure, vibrational spectra and electronic structure. The energy and composition of the frontier orbitals resemble those containing internal heteroatoms of preceding periods. We found that the diameter of the encapsulated internal{XO4}subunit varies as X does, while{M12O36}size and distances remain almost constant along the series. Vibrational modes calculations show that exist a dependency of the frequency and the anionic charge, nature of the heteroatom X and calculation methodology. Energy decomposition analysis of the{XO4}–{M12O36}interaction shows a predominant ionic character due to the high charge of the{XO4}anionic subunit. COSMO solvation model enabled us to compare heteropolyanions with different total charges. Our results suggest the possibility that these Keggin anions should be stable, being a new challenge for synthetic inorganic chemists.

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KW - Heteroplyanions

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