Charge disproportionation in RNiO3 (R = Tm, Yb) perovskites observed in situ by neutron diffraction and 57Fe probe Mossbauer spectroscopy

被引:32
作者
Alonso, J. A. [1 ]
Martinez-Lope, M. J. [1 ]
Presniakov, I. A. [2 ]
Sobolev, A. V. [2 ]
Rusakov, V. S. [2 ]
Gapochka, A. M. [2 ]
Demazeau, G. [3 ]
Fernandez-Diaz, M. T. [4 ]
机构
[1] CSIC, Inst Ciencia Mat Madrid, E-28049 Madrid, Spain
[2] Moscow MV Lomonosov State Univ, Moscow 119992, Russia
[3] Univ Bordeaux 1 Sci & Technol, ICMCB CNRS, F-33608 Pessac, France
[4] Inst Max Von Laue Paul Langevin, F-38042 Grenoble, France
基金
俄罗斯基础研究基金会;
关键词
METAL-INSULATOR-TRANSITION; RARE-EARTH; POWDER DIFFRACTION; TEMPERATURE; LU; SM; EVOLUTION; NUCLEAR; CAFEO3; YNIO3;
D O I
10.1103/PhysRevB.87.184111
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
An in-situ investigation from high-resolution neutron powder diffraction data on the structural evolution of TmNiO3 and YbNiO3 perovskites across the metal-insulator transition, with T-MI = 596 K and 598 K, respectively, allowed the charge disproportionation effect that these perovskites experience upon electronic localization below T-MI to be followed. In the insulating (semiconducting) regime, the perovskites are monoclinic, space group P2(1)/n, containing two inequivalent Ni1((3+sigma)+) and Ni2((3-sigma)+) cations; above T-MI, the samples become orthorhombic, space group Pbnm, with a single site for Ni3+. The Fe-57 Mossbauer spectra of iron-doped (at 1.5%) RNiO3 (R = Tm, Yb) samples recorded below T-MI exhibit for Fe1 and Fe2 (replacing Ni1 and Ni2 sites) hyperfine parameters corresponding to large (Ni1O(6)) and small (Ni2O(6)) octahedra. The remarkable difference between the quadrupole splittings (Delta(1) approximate to 0.3 mm/s and Delta(2) approximate to 0.07 mm/s) of Fe1 and Fe2 sites in RNi0.985Fe0.015O3 is analyzed. We calculate the lattice contribution to the electric field gradient (EFG) at Fe-57 ions, and estimate, by using the experimental Delta(1) and Delta(2) values, the contributions of the 3d, 3p, and 2p electrons (overlap distortion and covalence effects). Above T-MI, a unique state for iron atoms is observed, upon metallization of the sample.
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页数:12
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