Determinação da estrutura local de sítios do íon Eu3+ com alta simetria em cristais

Abstract

A study of the local structure of the Eu3+ ion with high symmetry in crystals was carried out using the crystal field theory by the method of nearest neighbours (MENN). The crystals studied were: M2O3, SnO2, BaliF3 and XMgF3 doped with very low concentrations of Eu3+ ion. From equations of the crystal field parameters, the maximum splitting of 7F1 multiplet and the electrostatic equilibrium of luminescent site was possible to predict the interatomic distance Eu-O ions in the luminescent site. For the M2O3 crystal, the overlap between the 4f orbitals and 2p in the range 0.07. Ïj.0.1 and the charge factor between 0.55.gj.0.9 gave better predictions for the indication of the local structure of luminescent site. The electrical neutrality of the luminescent site was satisfied. The Batista-Longo Improved Model (BLIM) was used to show that the Eu3+ ion charge may be greater than its own valence. The predictions give an indication of a point symmetry S6 or D3d. For the SnO2 oxide two sets of charge factors were used. Both were related by the equation of the electrostatic equilibrium of luminescent site. A P = 1.0029 proportionality constant related non equivalent interatomic distances. The overlap between the 4f orbitals and 2p in the range 0.05. Ïj.0.1 and the charge factor 0.5.gj.0.75 gave better predictions for the indication of the local structure of luminescent site. The predictions indicate that the Eu3+ ion replaces the Sn4+ ion in a point symmetry C2h or D2h. For the BaliF3 and XMgF3 crystals is suggested that the Eu3+ ion occupies a lowest symmetry D4d with coordination number eight. The experimental splitting was reproduced with gj = 0.402 and Ïj = 0.05. The signal of the B2 0 was reproduced. This study was done based on the emission spectrum of Eu3+ ion and structure calculations based on molecular dynamics. The predictions of the Eu-PV interatomic distance and local symmetry of the luminescent site is in good agreement with experimental data.