title: 51V magic-angle-spinning NMR and electric field gradient calculations in V2O5 and gamma-LiV2O5 crystals.
abstract: 51V Magic-angle-spinning (MAS) NMR has been applied to V2O5 at two different magnetic field strengths (4.7 and 7.1 T). Both the magnitude and relative orientation of the quadrupole and chemical shift (CS) tensors have been determined by iterative fitting of the 51V MAS NMR lineshapes at the two magnetic field strengths. The reliability of the results is discussed. Moreover, it is shown that previous low-field single-crystal data are fully consistent with the high-field powder-sample MAS NMR results provided that a slight noncoincidence between the CS tensor and the crystal frame axes is considered. The electric field gradient tensor at the vanadium and lithium sites is subsequently used to test several electronic structure calculation at an ab initio Hartree-Fock level in V2O5 and gamma-LiV2O5 crystals. It is shown that a wide distribution of oxygen charges must be considered to describe the particular environment of each type of oxygen atoms. Furthermore, this analysis supports the fact that the vanadyl bond is likely a short ionic bond. NMR is found to be a valuable experimental tool to get insight into the nature of chemical bonds in vanadium oxides.
authors.affiliation: Institut de Chimie, UMR 50 CNRS, Université Louis Pasteur, Strasbourg, France.
authors.forename: C
authors.initials: C
authors.lastname: Marichal
authors.forename: J Y
authors.initials: JY
authors.lastname: Kempf
authors.forename: B
authors.initials: B
authors.lastname: Maigret
authors.forename: J
authors.initials: J
authors.lastname: Hirschinger
mesh_terms: D003460:Crystallization; D009682:Magnetic Resonance Spectroscopy; D017968:Vanadium Compounds / Q000737:chemistry*
chemical_list: D017968:Vanadium Compounds; C066075:vanadium pentoxide