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

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