A study of the host lattice effect in the lanthanide hydroxides. 34 GHz Gd3+ impurity ion EPR spectra at 77 and 294 K

Abstract

The 34 GHz EPR spectra of 5-state (4f7, 8S) Gd3+ impurity ions (~1%) in the isostructural [Formula: see text] symmetry Ln(OH)3 host lattice (Ln ≡ La, Sm, Eu, Tb, Ho, Y) have been studied at 77 and 294 K. The expected seven line ΔM = ± 1 spectrum is observed for Ln = La, Eu, Ho, and Y whereas only a single broad transition is observed for Ln ≡ Sm and Tb. The observed values of the zero field splitting (ZFS) parameter B20 as well as the TZFS are found to be related linearly to (i) the ionic radius, (ii) the Ln–O1 distance, and (iii) the Ln–O2 distance where O1 and O2 are the nearest neighbour equatorial and apical oxygens. However, the slopes are opposite to that predicted by a point charge lattice model. This paper discusses (i) the SH parameters, (ii) the host lattice effect, (iii) the ZFS processes, and (iv) the linewidths observed in the Ln(OH)3 host lattice and attempts to explain the observations using the existing theory. It is found that this apparently simple host lattice exhibits complex effects which do not change systematically with the host lanthanide ion, unlike that observed in most other isostructural lanthanide hosts that have been studied using Gd3+ impurity ions.