doi:10.1016/j.nimb.2005.12.037
Copyright © 2005 Elsevier B.V. All rights reserved.
Quantitative structural refinement of Mn K edge XANES in LaMnO3 and CaMnO3 perovskites
C. Monesia, C. Meneghinia, b,
,
, F. Bardellia, b, M. Benfattoc, S. Mobilioa, b, c, U. Manjud and D.D. Sarmad
aDipartimento di Fisica, Universitá di “Roma Tre”, Via Della Vasca Navale, 84, I-00146 Roma, Italy
bINFM-GILDA, c/o ESRF, Grenoble, France
cINFN Laboratori Nazionali di Frascati, Via E. Fermi 40, I-00044 Frascati, Italy
dSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India
Available online 30 January 2006.
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Abstract
The special magnetotransport properties of hole doped manganese perovskites originate from a complex interplay among structural, magnetic and electronic degree of freedom. In this picture the local atomic structure around Mn ions plays a special role and this is the reason why short range order techniques like X-ray absorption spectroscopy (XAS) have been deeply exploited for studying these compounds. The analysis of near edge region features (XANES) of XAS spectra can provide very fine details of the local structure around Mn, complementary to the EXAFS, so contributing to the full understanding of the peculiar physical properties of these materials. Nevertheless the XANES analysis is complicated by the large amount of structural and electronic details involved making difficult the quantitative interpretation.
This work exploits the recently developed MXAN code to achieve a full structural refinement of the Mn K edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1−xMnO3, in which the Mn ions are present only in one charge state as Mn3+ and Mn4+ respectively. The good agreement between the results derived from the analysis of near edge and extended region of the XAS spectra demonstrates that a quantitative picture of the local structure can be obtained from structural refinement of Mn K edge XANES data in these crystalline compounds. The XANES analysis offers, in addition, the possibility to directly achieve information on the topology of local atomic structure around the absorber not directly achievable from EXAFS.
Keywords: XANES; Colossal-magnetoresistance; Structure
PACS classification codes: 61.10.Ht; 75.47.Lx; 73.43.Qt
Fig. 2. EXAFS fitting results. Left: experimental data (points) and best fit are shown in k-space for CaMnO3 (upper panel) and LaMnO3 (lower panel). The residual k(χexp − χth) are shown, shifted for clarity. Right: the moduli and imaginary parts (shifted for clarity) of Fourier transforms of experimental (points) and theoretical (lines) EXAFS data for CaMnO3 (upper panel) and LaMnO3 (lower panel).
Fig. 1. Schematic view of La(Ca)MnO3 local structure around the absorber (Mn0).
Fig. 3. XANES fitting for LaMnO3 (left panels) and CaMnO3 (right panels): the experimental data are shown as lines-points, the theoretical curves are reported as full lines, residuals (experimental–theory) are shown, shifted for clarity. Upper curves (a): the initial models as obtained from the crystallographic structure only refining the potential parameters, lower curves (b): the final best fit. The secondary edge contributions to the background are also shown for completeness.
Fig. 4. Upper right: Mn–Ca1 and distributions as derived from diffraction data (XRD) compared with XANES and EXAFS results. Lower left: Mn–O1 distributions in LaMnO3 as given from crystallography (XRD) compared with XANES and EXAFS results. Lower right: Mn–La1 distributions in LaMnO3 as given from crystallography (XRD)compared with XANES and EXAFS results.
Table 1.
Mn-local structure on CaMnO3 and LaMnO3 samples as resulting from EXAFS analysis

The errors on the last digit on refined parameters are reported in parentheses.
a The Debye–Waller factors for single (SS), double (S
2) and triple (S
3) scattering were the same.
b The Mn–O
1–Mn
1 bond angle is calculated as:
θO1=2sin-1(RSS/RS3) with

and
RSS=RS3-2δ.
Table 2.
The main structure features characterizing the Mn local atomic environment in CaMnO3 and LaMnO3 samples as obtained from XANES structural refinement

Table 3.
The main structural features of LaMnO3 and CaMnO3 samples as obtained by EXAFS and XANES analysis are compared with the crystallographic structure 
