Infrared and Raman spectroscopic and theoretical studies of nonaaqua complexes of trivalent rare earth metal ions

János Mink, Mikhail Yu Skripkin, László Hajba, Csaba Németh, Alireza Abbasi, Magnus Sandström

Research output: Contribution to journalArticle

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Abstract

Infrared (IR), far-infrared (far-IR) and Raman spectra have been recorded of the hydrated lanthanide(III) trifluoromethanesulfonates, [Ln(OH 2)9](CF3SO3)3, (Ln = La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu), and also for the deuterated [La(OD2)9](CF3SO3)3 compound. This has enabled complete assignments of all seven metal-oxygen stretching modes for the first time. Force constant calculations have been performed for an LnO93+ moiety, with a tricapped trigonal prismatic oxygen atom arrangement in D3h point group symmetry. The lanthanide contraction in reflected in continuously increasing trends for the averaged LnO stretching frequencies and force constants with increasing inverse of ionic radii. The stretching force constants increased from 0.81 to 1.16 Ncm-1 for the LnO6 prism in the series from La to Lu, while those for the capping LnO3 bonds increased from 0.49 to 0.65 Ncm-1. The LnO stretching force constants showed a smooth correlation with the LnO bond distances to the prism oxygen atoms, while the correlation to the LnO capping oxygen atoms has a different shape, reflecting the increased ligand-ligand repulsion with decreasing lanthanide ion size.

Original languageEnglish
Pages (from-to)1639-1645
Number of pages7
JournalSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Volume61
Issue number7
DOIs
Publication statusPublished - May 2005

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Rare Earth Metals
Lanthanoid Series Elements
Rare earths
Stretching
Metal ions
metal ions
rare earth elements
Rare earth elements
Oxygen
Infrared radiation
Prisms
oxygen atoms
Atoms
Ligands
prisms
Point groups
Crystal symmetry
ligands
Raman scattering
Metals

Keywords

  • Far-infrared spectra
  • Force constants
  • Infrared
  • Nonaaqua- lanthanide(III) complexes
  • Raman

ASJC Scopus subject areas

  • Spectroscopy

Cite this

Infrared and Raman spectroscopic and theoretical studies of nonaaqua complexes of trivalent rare earth metal ions. / Mink, János; Skripkin, Mikhail Yu; Hajba, László; Németh, Csaba; Abbasi, Alireza; Sandström, Magnus.

In: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, Vol. 61, No. 7, 05.2005, p. 1639-1645.

Research output: Contribution to journalArticle

Mink, János ; Skripkin, Mikhail Yu ; Hajba, László ; Németh, Csaba ; Abbasi, Alireza ; Sandström, Magnus. / Infrared and Raman spectroscopic and theoretical studies of nonaaqua complexes of trivalent rare earth metal ions. In: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy. 2005 ; Vol. 61, No. 7. pp. 1639-1645.
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AB - Infrared (IR), far-infrared (far-IR) and Raman spectra have been recorded of the hydrated lanthanide(III) trifluoromethanesulfonates, [Ln(OH 2)9](CF3SO3)3, (Ln = La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu), and also for the deuterated [La(OD2)9](CF3SO3)3 compound. This has enabled complete assignments of all seven metal-oxygen stretching modes for the first time. Force constant calculations have been performed for an LnO93+ moiety, with a tricapped trigonal prismatic oxygen atom arrangement in D3h point group symmetry. The lanthanide contraction in reflected in continuously increasing trends for the averaged LnO stretching frequencies and force constants with increasing inverse of ionic radii. The stretching force constants increased from 0.81 to 1.16 Ncm-1 for the LnO6 prism in the series from La to Lu, while those for the capping LnO3 bonds increased from 0.49 to 0.65 Ncm-1. The LnO stretching force constants showed a smooth correlation with the LnO bond distances to the prism oxygen atoms, while the correlation to the LnO capping oxygen atoms has a different shape, reflecting the increased ligand-ligand repulsion with decreasing lanthanide ion size.

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