NMR study of the LiMnPO(4)·OH and MPO(4)·H(2)O (M = Mn, V) homeotypic phases and DFT calculations

• Published in: Solid state nuclear magnetic resonance 2012-04, Vol.42, p.42-50
• Main Authors: Castets, A, Carlier, D, Zhang, Y, Boucher, F, Marx, N, Gautier, R, Le Fur, E, Le Pollès, L, Croguennec, L, Ménétrier, M
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Computer Simulation; Ions; Lithium - chemistry; Lithium Compounds - chemistry; Magnetic Resonance Spectroscopy - methods; Material chemistry; Materials Testing - methods; Models, Chemical
• ISSN: 0926-2040; 1527-3326
• DOI: 10.1016/j.ssnmr.2011.11.001

Following our previous work on the tavorite-like LiFePO(4)·OH and FePO(4)·H(2)O phases, we report here the magnetic and NMR characterizations of analogous LiMnPO(4)·OH, MnPO(4)·H(2)O and VPO(4)·H(2)O phases together with the DFT calculations of the NMR shifts. The first two compounds exhibit Curie-Weiss type magnetic behavior with Curie constants close to the theoretical ones for HS Mn(3+), while the vanadium compound is very close to a pure Curie-type behavior. (7)Li, (31)P and (1)H MAS NMR spectra are reported for the three compounds, and show strong Fermi-contact shifts for the first two nuclei, while the sign and magnitude of the (1)H shifts are very different for the three phases. DFT calculations (FLAPW in GGA+U approximation) using the WIEN2k code and the experimental susceptibilities are shown to reproduce closely the experimental data. This situation is compared to the case of the homologous and isostructural Fe compounds, which exhibit much more complex magnetic behaviors.