A combination of 169Tm-Mo??ssbauer spectroscopy and inelastic neutron scattering (INS) has been used to investigate the crystal field (CF) interaction at the rare earth site for the tetragonal series RT2Si2 (where R = rare earth) and the orthorhombic series RNiAl4. Single phase specimens were prepared in an argon arc furnace and characterised using x-ray powder diffraction, specific heat and magnetic measurements. For the RT2Si2 series previous investigations were extended to include T = Mn and Cr whose sub-lattices are antiferromagnetic well above room temperature. However, the rare earth sub-lattices were confirmed to order close to liquid helium temperature. With the assistance of the lattice electric field gradient (EFG) for isostructural GdCr2Si2 (determined elsewhere using 155Gd-Mo??ssbauer spectroscopy) and the within-rank CF parameter ratios for HoCr2Si2 (determined elsewhere using INS), the experimental 169Tm quadrupole interaction data were analysed to arrive at CF parameters for the Tm3+ site in TmCr2Si2. The final CF parameters match well with the trend observed for other members of the series RT2Si2 (T = Fe, Co, Ni, Cu). CF schemes were also determined for Tm3+ in TmMn2Si2 and Er3+ in both ErCr2Si2 and ErMn2Si2. For the RNiAl4 series, TmNiAl4 was determined to be antiferromagnetic below TN = 4.7 K with the 169Tm-Mo??ssbauer spectra retaining a magnetic appearance up to 80 K due to the effect of slow spin-lattice relaxation. The relaxation data are consistent with a well-isolated ground state doublet (or pseudo-doublet) whose eigenfunctions have high components of mJ = ??6 states and with the relaxation proceeding via an excited state at 350 K. Because of the relaxation effect, the 169Tm-Mo??ssbauer data could not be interpreted in terms of CF parameters in the usual way. Instead, the INS spectra recorded for ErNiAl4 were analysed using a novel semi-empirical approach that coupled rank 2 CF parameters converted from the EFG tensor for isostructural GdCr2Si2 (determined elsewhere using 155Gd-Mo??ssbauer spectroscopy) with simple point-charge model calculations of the rank 4 and 6 within-rank CF parameter ratios. The first full set of CF parameters for this series was then determined for the Er3+ site in ErNiAl4.
| Identifer | oai:union.ndltd.org:ADTP/258757 |
| Date | January 2009 |
| Creators | Saensunon, Banchachit, Physical, Environmental & Mathematical Sciences, Australian Defence Force Academy, UNSW |
| Publisher | Awarded by:University of New South Wales - Australian Defence Force Academy. Physical, Environmental & Mathematical Sciences |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | http://unsworks.unsw.edu.au/copyright |
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