A high-precision electron paramagnetic resonance study of Gd3+ in single crystals of the lanthanide ethyl sulfate nonahydrates near room temperature

Abstract

By methods described by Gerkin and Rogers [J. Chem. Phys. 66, 4166 (1977)], high precision values of the spin-Hamiltonian parameters b20, b40, and b60, and of the zero-field splittings, for Gd3+ dilutely substituted in single crystals of 13 lanthanide ethyl sulfate nonahydrates at room temperature (24.130° C) are presented. Since sample shape dependence is significant at the reported level of precision, the measured values were adjusted to yield corresponding values for spherical samples via the analysis of shape dependence presented by Gerkin and Rogers [J. Chem. Phys. 68, 504 (1978)]. Correlations of b20, b40, and b60, and of the zero-field splittings, with the ionic radii of the host lanthanides are presented and compared with previous results. Values of the intrinsic parameter ?2 of the superposition model analysis of b20 are obtained for Gd3+ in these salts and are displayed as a function of host ionic radius. The value −3.0 was obtained for the superposition model parameter t2. More detailed analysis of these parameters will require improved knowledge of the rare earth trivalent ion radii and of ion–ligand distances in the ethyl sulfate nonahydrate series.

The structures of the lanthanide ethyl sulfate enneahydrates, M(C2H5SO4)3.9H2O [M = La–Lu (except Pm)], at 171 K

“…A detailed knowledge of the host crystal structure and the use of the superposition model (Newman & Urban, 1972) allows the determination of hostindependent spin-Hamiltonian parameters for a paramagnetic ion. Such an analysis was done for Gd TM in the lanthanide ethyl sulfates by Gerkin & Rogers (1979), using the limited structural data then available. This comprehensive examination of the lanthanide ethyl sulfate series (except promethium) was undertaken in part to provide accurate geometric details for each structure, so that an improved superposition model analysis could be performed for Gd HI in this crystal series.…”

Host‐Lattice Effects in the EPR Spectra of Gd3+ Doped Hydrated Single Crystals of Rare‐Earth Chlorides, Nitrates, and Sulphates

“…1 and RES ([4] to [8]) hosts. As for the parameter bi, which is certainly non-linear in the host-ion radius for the R T F hosts (for the RES hosts 6: vanishes due to the site symmetry), it is also found from and bg for some hosts from those which would satisfy exact linearity in host ion radius for the various host families may be due to the much different unit cell parameters for these hosts as compared to others in the family.…”