Crystal Field Determination in Rare‐Earth Oxysulfides. I. Optical Experiments for Tb 3+ Ion

The paper, as the third in a series, presents the complete formulas for the crystal field splitting third moment of free ion states as functions of the relevant crystal field parameters in the case of the trigonal and hexagonal crystal fields. The additive structure of the expressions consists of 21 independent components for the trigonal symmetry, 12 for the hexagonal one and only 4 components for the ideal hexagonal coordination. The two scalar characteristics of the crystal field Hamiltonian H CFthe crystal field splitting second and third momentsenable us to verify the H CF parametrizations solely in an algebraic way. Such verification concerns the multipolar structure of the parametrizations as well as the signs of the crystal field parameters. Both the crystal field splitting moments can ensure us in what degree the comprehensive H CF parametrizations are adequate with respect to the individual ionic states of the electron configuration. As an example two chosen H CF parametrizations, one for the hexagonal system Nd 3þ :LaCl 3 of the C 3h symmetry, and the second for the trigonal system Tb 3þ :Y 2 O 2 S of the C 3v symmetry are subjected to in depth analysis. The presented approach provides a critical insight into the crystal field parametrizations from a different point of view, i.e., omitting the conventional fitting procedure. After the extended verification the studied classical H CF parametrizations withstand, in principle, the test of time.

Section: A Trial Of Algebraic Verification Of the H Cf Parametrizatiosupporting

confidence: 89%

Section: Introductionmentioning

confidence: 95%

Section: A Trial Of Algebraic Verification Of the H Cf Parametrizatiomentioning

confidence: 99%

Section: A Trial Of Algebraic Verification Of the H Cf Parametrizatiomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

The Second and Third Crystal Field Splitting Moments in Verification of the Trigonal and Hexagonal Crystal Field Parametrizations

Mulak

2018

Crystal Field Determination in Rare‐Earth Oxysulfides. II. Optical Experiments for Ho³⁺ and Dy³⁺ Ions

Rossat‐Mignod¹,

Souillat²,

Quézel³

1974

Self Cite

The crystal field levels of the ground state manifold of Ho3+ have been obtained from the luminescence spectrum of Yz02S:5~o Ho3+. The ground state of the Ho3+ ion is found to be a set of five levels (0, 8, 14, 18,23 cm-1). An attempt has been made t o deduce the parameters of the CEF Hamiltonian from the experimental level energies. For Dy3+, the breaking up of the fundamental 'H15/2 multiplet has been obtained by analysing the fluorescence spectrum of Y202S: 1% Dy3+ and the absorption spectrum of Dy20,S. The ground state is found to be a doublet relatively well separated (21 cm-1) from the first excited level. I n these two compounds, CEF calculations give satisfactory agreement with both the value and direction of the magnetic moment obtained from neutron diffraction experiments.Les niveaux de champ cristallin du multiplet fondamental &I8 dc l'ion Ho3+ ont BtB obtenues par l'analyse du spectre de luminescence de Y202S:5~0 Ho3+. L'btat fondamental est constitub d'un ensemble de 5 niveaux trhs serrbs (0, 8, 14, 18, 23 cm-l). Sur la base de ces rbsultats cxpbrimentaux, nous avons dCterminB les six parametres de I'hitmiltonien de champ cristallin. En ce qui concerne Dy3+, la dbcomposition du multiplet fondamental 6H15/2 a Btb dbduite du spectre de fluorescence de YzO,S: l"/b Dy3+ et d u spectre d'absorption du composb pur. L'btat fondamental est un doublet relativement bien sbparb (21 cm-l) du premier niveau excitb. Pour ces deux composbs, les calculs de champ cristallin sont en accord satisfaisant avec les rbsultats de diffraction neutroniqoe, en ce qui concerne la direction et la vnleir des moments magnbtiqries.

Crystal Field Determination in Rare‐Earth Oxysulfides III. Specific Heat Measurements on Gd, Tb, Ho, and Dy Oxysulfides

Rossat‐Mignod¹,

Quézel

Berton³

et al. 1974

Self Cite

The specific heat of gadolinium, terbium, dysprosium, and holmium oxysulfides has been measured between 1.4 and 80 K. The lattice contribution has been obtained by the analysis of the Gd,O,S results. For the terbium, dysprosium, and holmium oxysulfides, the specific heat studies allowed to remove the ambiguities of the optical measurements and to precise the crystal field splitting of the rare-earth ground state multiplet.La chaleur spkcifique des oxysulfures de gadolinium, terbium. dysprosium et holmium a kt6 mesurke entre 1,4 et 80 K. L'analyse des rksultats relatifs B Gd20,S nous a permis d'obtenir la contribution du rkseau. Pour les oxysulfures de terbium, dysprosium et holmium. I'ittude de la chaleur sphcifique a permis de lever les ambiguites des mesures optiques et de preciser la dkcomposition du multiplet fondamental des ions terre rare par le champ cristallin.