[en] Several compounds of the NaMn(Fe1-xInx)(2)(PO4)(3) solid solution were synthesized by solid state reaction in air; pure alluaudite-like compounds were obtained for x = 0.00 to 1.00. X-ray Rietveld refinements indicate the presence of Na+ at the A1 and A2' sites, Mn2+ at the M1 site, and Fe2+, Fe3+, and In3+ at the M2 site. The presence of small amounts of In3+ at the M I site, and Mn2+ at the M2 site, indicates a partially disordered distribution between these cations. A good correlation was also established between the M1-M2 bond distance and the beta angle of the alluaudite-like compounds. The disordered distribution of Fe2+, Fe3+, and In3+ at the M2 site is confirmed by the broadness of the infrared absorption bands. The Mossbauer spectra, measured between 90 and 295 K, were analyzed in terms of a model that takes into account the next-nearest neighbor interactions around the M2 crystallographic site. In all cases these spectra reveal the unexpected presence of small amounts of Fe2+ at the M2 site, an amount that decreases as the In3+ content increases. The Fe2+ and Fe3+ isomer shifts are typical of the alluaudite structure and vary with temperature, as expected from a second-order Doppler shift. The derived iron vibrating masses and Mossbauer lattice temperatures are within the expected range of values for iron cations in an octahedral environment. The Fe2+ and Fe3+ quadrupole splittings are also typical of the alluaudite structure and the temperature dependence of the Fe2+ quadrupole splitting was fit with the model of Ingalls (1964), which yielded a ground state orbital splitting of ca. 380 to 570 cm(-1) for the Fe2+ sites.
Disciplines :
Chemistry Earth sciences & physical geography
Author, co-author :
Hatert, Frédéric ; Université de Liège - ULiège > Département de géologie > Minéralogie et cristallochimie
Hermann, Raphaël ; Université de Liège - ULiège > Département de physique > Département de physique
Long, Gary J.; University of Missouri-Rolla > Department of Chemistry
Fransolet, André-Mathieu ; Université de Liège - ULiège > Département de géologie > Minéralogie et cristallochimie
Grandjean, Fernande ; Université de Liège - ULiège > Département de physique > Département de physique
Language :
English
Title :
An X-ray Rietveld, infrared, and Mossbauer spectral study of the NaMn(Fe1-xInx)(2)(PO4)(3) alluaudite-type solid solution
Publication date :
2003
Journal title :
American Mineralogist
ISSN :
0003-004X
Publisher :
Mineralogical Soc Amer, Washington, United States - District of Columbia
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