Relationship between phenomenological crystal field parameters and the crystal structure: The simple overlap model

Porcher, P.; Santos, Marcos Couto Dos; Malta, O.L.

doi:10.1039/a803807d

Cited by 119 publications

(85 citation statements)

References 40 publications

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“…More recently a quantitative determination of crystal-field parameters for such lanthanide ions [36] has been achieved through the use of the simple overlap model, [37] an extension of purely electrostatic ligandfield theory taking into account some degree of covalence. With the assumption of isotropic coupling, a reasonable fit of the powder susceptibility data was realized in the case of anisotropic lanthanide ions like Dy III and Ho III .…”

Section: Resultsmentioning

confidence: 99%

Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of Yb^III Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

Pointillart

Cauchy

Maury

et al. 2010

Chemistry A European J

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The tetrathiafulvalene-amido-2-pyridine-N-oxide (L) ligand has been employed to coordinate 4f elements. The architecture of the complexes mainly depends on the ionic radii of the lanthanides. Thus, the reaction of L in the same experimental protocol leads to three different molecular structure series. Binuclear [Ln(2)(hfac)(5)(O(2)CPhCl)(L)(3)]·2 H(2)O (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion, O(2)CPhCl(-)=3-chlorobenzoate anion) and mononuclear [Ln(hfac)(3)(L)(2)] complexes were obtained by using rare-earth ions with either large (Ln(III)=Pr, Gd) or small (Ln(III)=Y, Yb) ionic radius, respectively, whereas the use of Tb(III) that possesses an intermediate ionic radius led to the formation of a binuclear complex of formula [Tb(2)(hfac)(4)(O(2)CPhCl)(2)(L)(2)]. Antiferromagnetic interactions have been observed in the three dinuclear compounds by using an extended empirical method. Photophysical properties of the coordination complexes have been studied by solid-state absorption spectroscopy, whereas time-dependent density functional theory (TD-DFT) calculations have been carried out on the diamagnetic Y(III) derivative to build a molecular orbital diagram and to reproduce the absorption spectrum. For the [Yb(hfac)(3)(L)(2)] complex, the excitation at 19,600 cm(-1) of the HOMO→LUMO+1/LUMO+2 charge-transfer transition induces both line-shape emissions in the near-IR spectral range assigned to the (2)F(5/2)→(2)F(7/2) (9860 cm(-1)) ytterbium-centered transition and a residual charge-transfer emission around 13,150 cm(-1). An efficient antenna effect that proceeds through energy transfer from the singlet excited state of the tetrathiafulvalene-amido-2-pyridine-N-oxide chromophore is evidence of the Yb(III) sensitization.

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Section: Resultsmentioning

confidence: 99%

Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of Yb^III Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

Pointillart

Cauchy

Maury

et al. 2010

Chemistry A European J

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“…It has been successfully applied to reproduce the phenomenological cfp's for a great number of lanthanides as well as for some 3d element compounds (12)(13)(14)(15). In this model, the cfp's are calculated from the atomic positions in the structure and are written as…”

Section: The Simple Overlap Modelmentioning

confidence: 99%

The Family of Ln2Ti2S2O5 Compounds (Ln=Nd, Sm, Gd, Tb, Dy, Ho, Er, and Y): Optical Properties

Boyer‐Candalen

Derouet²,

Porcher³

et al. 2002

Journal of Solid State Chemistry

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“…Using the Simple Overlap Model [11,12], the crystal field parameters values show that the inclusion of relaxation is important in the calculations, and the relative magnitudes suggest that the Ce 3+ doped system will show the strongest optical transitions. In a recent experimental study [13] The ultimate aim of these calculations is to provide a quick and efficient method to 'screen' host-dopant systems for potential use as optical materials.…”

Section: Crystal Field Calculationsmentioning

confidence: 98%

“…The simulation of that distortion leads to a new set of coordinates of the first neighbour ligand ions. Both non-distorted lattice coordinates and the coordinates obtained using the defect simulation technique are used to calculate the B k q parameters using the simple overlap model (SOM) [11,12]. The new set of non-zero crystal field parameters from the defect simulation calculation determines the actual rare earth ion local symmetry, and can be used to predict the optical emission lines for a given dopant-host system.…”

Section: Crystal Field Backgroundmentioning

confidence: 99%

Computer modelling of the optical behaviour of rare earth dopants in BaY ₂ F ₈

Jackson

Valério

Santos

et al. 2005

phys. stat. sol. (c)

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BaY 2 F 8 , when doped with rare earth elements is a material of interest in the development of solid-state laser systems, especially for use in the infrared region. This paper presents the application of a new computational technique, which combines atomistic modelling and crystal field calculations in a study of rare earth doping of the material. Atomistic modelling is used to calculate the symmetry and detailed geometry of the dopant ion-host lattice system, and this information is then used to calculate the crystal field parameters, which are an important indicator in assessing the optical behaviour of the dopant-crystal system. Comparisons with the results of recent experimental work on this material are made.

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Relationship between phenomenological crystal field parameters and the crystal structure: The simple overlap model

Cited by 119 publications

References 40 publications

Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of Yb^III Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of Yb^III Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

The Family of Ln2Ti2S2O5 Compounds (Ln=Nd, Sm, Gd, Tb, Dy, Ho, Er, and Y): Optical Properties

Computer modelling of the optical behaviour of rare earth dopants in BaY ₂ F ₈

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Relationship between phenomenological crystal field parameters and the crystal structure: The simple overlap model

Cited by 119 publications

References 40 publications

Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of YbIII Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of YbIII Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

The Family of Ln2Ti2S2O5 Compounds (Ln=Nd, Sm, Gd, Tb, Dy, Ho, Er, and Y): Optical Properties

Computer modelling of the optical behaviour of rare earth dopants in BaY 2 F 8

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Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of Yb^III Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of Yb^III Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

Computer modelling of the optical behaviour of rare earth dopants in BaY ₂ F ₈