Covalent bonding and J–J mixing effects on the EPR parameters of Er^(3+) ions in GaN crystal

The EPR parameters of trivalent Er（3＋） ions doped in hexagonal Ga N crystal have been studied by diagonalizing the 364×364 complete energy matrices. The results indicate that the resonance ground states may be derived from the Kramers doublet Γ6. The EPR g-factors may be ascribed to the stronger covalent bonding and nephelauxetic effects compared with other rare-earth doped complexes, as a result of the mismatch of ionic radii of the impurity Er（3＋）ion and the replaced Ga（3＋） ion apart from the intrinsic covalency of host Ga N. Furthermore, the J–J mixing effects on the EPR parameters from the high-lying manifolds have been evaluated. It is found that the dominant J–J mixing contribution is from the manifold 2K（15/2）, which accounts for about 2.5%. The next important J–J contribution arises from the crystal–field mixture between the ground state 4I（15/2） and the first excited state4I（13/2）, and is usually less than 0.2%. The contributions from the rest states may be ignored.

Investigations of the electron paramagnetic resonance parameters and the tetragonal local structure for (VCl_6)^(4-) coordination complex in MCl:V^(2+) (M=Na,K,Rb) systems

By simulating the electron paramagnetic resonance （EPR） and optical spectra on the basis of the 120 × 120 complete energy matrix, this paper determines the local lattice structure parameters R1 and R2 for MCl：V2＋ （M=Na, K, Rb） systems at 77K, 195 K and RT （room temperature 295 K or 302 K）, respectively. The theoretical results indicate that there exists a compressed distortion in MCl：V2＋ systems. Meanwhile, it finds that the structure parameters R1, R2 and ｜△R｜（ = R1 - R2） increase with the rising temperature. Subsequently, from the analysis it concludes that the relation of EPR parameter D vs. △R is approximately linear. Finally, the effects of orbital reduction factor k on the g factors for the three systems have been discussed.

Determination of charge-compensated C3v (Ⅱ) centers for Er3+ ions in CdF2 and CaF2 crystals

A unified theoretical method is established to determine the charge-compensated C3v(Ⅱ)centers of Er3+ions in CdF2 and CaF2 crystals by simulating the electron paramagnetic resonance(EPR)parameters and Stark energy levels.The potential(Er^(3+)–F^(−)–O_(4)^(2−))and(Er^(3+)-F_(7)^(−)-O_(4)^(2−))structures for theC3v(Ⅱ)centers of Er3+ions in CdF2 and CaF2 crystals are checked by diagonalizing 364×364 complete energy matrices in the scheme of superposition model.Our studies indicate that the C3v(Ⅱ)centers of Er3+ions in CdF2 and CaF2 may be ascribed to the local(Er^(3+)-F^(−)-O_(4)^(2−))structure,where the upper ligand ion F−undergoes an off-center displacement by∆Z≈0.3˚A for CdF2 and∆Z≈0.29˚A for the CaF2 along the C3 axis.Meanwhile,a local compressed distortion of the(ErFO4)6−cluster is expected to be∆R≈0.07˚A for CdF2:Er3+and∆R≈0.079˚A for CaF2:Er3+.The considerable g-factor anisotropy for Er3+ions in each of both crystals is explained reasonably by the obtained local parameters.Furthermore,our studies show that a stronger covalent effect exists in the C3v(Ⅱ)center for Er3+in CaF2 or CaF2,which may be due to the stronger electrostatic interaction and closer distance between the central Er3+ion and ligand O2−with the(Er^(3+)-F^(−)-O_(4)^(2−))structure.

First-principles calculations and re-analysis of optical spectra and electron paramagnetic resonance parameters for Yb3＋ in YAl3BO34 crystal

In this paper,the energy levels of Yb^（3＋） ions in yttrium aluminum borate（YAB） crystal were calculated from a first-principles approach with an optimized defect structure obtained from the WIEN2 k package and a traditional fitting method using a more reliable computer package.The calculated results were then compared with those obtained from a re-calculation using the values of parameters given by some previous researchers.Three types of likely mistakes in the previous researcher＇s paper,namely over fitting,incorrect use of irreducible representation,and errors in the calculations for the EPR parameters were clearly identified and effectively rectified in this paper.The electron paramagnetic resonance（EPR） parameters,which included g factors like g（//） and g⊥ and hyperfine structure constants A// and A⊥,were also calculated through the perturbation method and compared with some observed values available in literature.There was reasonable agreement found with the experimental values which lay between the values obtained from the first-principles calculation（g//=4.000 and g⊥=1.391;A//=1032 and A⊥=360 in 10^（-4） cm^（-1） for ^（171）Yb^（3＋）） and those from the fitting approach（g//=3.612 and g⊥=1.702;A//=867 and A⊥=470 in 10^（-4） cm^（-1） for ^（171）Yb^（3＋））.