Understanding Optical Absorption Spectra and Magnetic Behavior of a Wide Range of Samarium(III) Oxo‐Compounds: Analysis of the Ligand‐Field Effects

Abstract

AbstractIn this study powder reflectance spectra as well as temperature dependent magnetic susceptibilities of eight different samarium(III) oxo‐compounds (SmP5O14, SmPO4, SmVO4, SmNbO4, SmTaO4, Sm2Ti2O7, SmAsO4, B‐type Sm2O3 and C‐type Sm2O3) have been measured. In addition, high‐resolution electronic absorption spectra in the near infrared of single crystals of seven of these compounds are reported. Comparing our experimental data to the results of ligand field analyses (angular overlap model AOM allowing for decomposition of the global ligand field into the contributions of the individual ligands; computer program BonnMag) shows reasonable agreement of electronic transition energies in optical spectra and a good fit of the temperature dependent Bohr magneton numbers μeff/μB. Analysis of the ‘best fit’ AOM parameters reveals a significant variation in the nephelauxetic effect with F2=379 cm−1 for SmP5O14 and F2=356 cm−1 for KSmO2. A trend in the variation of the AOM parameter eσ with the optical basicity Λ is discussed. The values for eσ(Sm−O), normalized to d(Sm−O)=2.38 Å, range from 337 cm−1 for SmP5O14 to 573 cm−1 for KSmO2. For the ratio eπ/eσ only a negligible influence on the match between calculated and experimental data is observed. For the relation of eσ(Sm−O) to the interatomic distance d(Sm−O) the correlation eσ(Sm−O) ∼1/d7(Sm−O) was found to reproduce in AOM the observed ligand field splitting well. For SmPO4 a high resolution, low temperature (110 K) spectrum allows the assignment of hot bands.