Diffraction Anomalous Fine Structure Research Articles

Refinement of the uranium dispersion corrections from anomalous diffraction

The evolution of the uranium chemical state in uranium compounds, principally in the oxides, is of concern in the context of nuclear fuel degradation under storage and repository conditions, and in accident scenarios. The U–O system shows complicated phase relations between single-valence uranium dioxide (UO2) and different mixed-valence compounds (e.g. U4O9, U3O7 and U3O8). To try resolving the electronic structure associated with unique atomic positions, a combined application of diffraction and spectroscopic techniques, such as diffraction anomalous fine structure (DAFS), can be considered. Reported here is the application of two newly developed routines for assessing a DAFS data set, with the aim of refining the uranium X-ray dispersion corrections. High-resolution anomalous diffraction data were acquired from polycrystalline powder samples of UO2 (containing tetravalent uranium) and potassium uranate (KUO3, containing pentavalent uranium) using synchrotron radiation in the vicinity of the U L 3 edge (17.17 keV). Both routines are based on an iterative refinement of the dispersion corrections, but they differ in either using the intensity of a selection of reflections or doing a full-pattern (Rietveld method) refinement. The uranium dispersion corrections obtained using either method are in excellent agreement with each other, and they show in great detail the chemical shifts and differences in fine structure expected for tetravalent and pentavalent uranium. This approach may open new possibilities for the assessment of other, more complicated, materials such as mixed-valence compounds. Additionally, the DAFS methodology can offer a significant resource optimization because each data set contains both structural (diffraction) and chemical (spectroscopy) information, which can avoid the requirement to use multiple experimental stations at synchrotron sources.

Uncovering a CF3 Effect on X-ray Absorption Energies of [Cu(CF3 )4 ]- and Related Copper Compounds by Using Resonant Diffraction Anomalous Fine Structure (DAFS) Measurements.

Understanding the electronic structures of high-valent metal complexes aids the advancement of metal-catalyzed cross coupling methodologies. A prototypical complex with formally high valency is [Cu(CF3 )4 ]- (1), which has a formal Cu(III) oxidation state but whose physical analysis has led some to a Cu(I) assignment in an inverted ligand field model. Recent examinations of 1 by X-ray spectroscopies have led previous authors to contradictory conclusions, motivating the re-examination of its X-ray absorption profile here by a complementary method, resonant diffraction anomalous fine structure (DAFS). From analysis of DAFS measurements for a series of seven mononuclear Cu complexes including 1, here it is shown that there is a systematic trifluoromethyl effect on X-ray absorption that blue shifts the resonant Cu K-edge energy by 2-3 eV per CF3 , completely accounting for observed changes in DAFS profiles between formally Cu(III) complexes like 1 and formally Cu(I) complexes like (Ph3 P)3 CuCF3 (3). Thus, in agreement with the inverted ligand field model, the data presented herein imply that 1 is best described as containing a Cu(I) ion with dn count approaching 10.

Uncovering a CF3 Effect on X‐ray Absorption Energies of [Cu(CF3)4]− and Related Copper Compounds by Using Resonant Diffraction Anomalous Fine Structure (DAFS) Measurements**

AbstractUnderstanding the electronic structures of high‐valent metal complexes aids the advancement of metal‐catalyzed cross coupling methodologies. A prototypical complex with formally high valency is [Cu(CF3)4]− (1), which has a formal Cu(III) oxidation state but whose physical analysis has led some to a Cu(I) assignment in an inverted ligand field model. Recent examinations of 1 by X‐ray spectroscopies have led previous authors to contradictory conclusions, motivating the re‐examination of its X‐ray absorption profile here by a complementary method, resonant diffraction anomalous fine structure (DAFS). From analysis of DAFS measurements for a series of seven mononuclear Cu complexes including 1, here it is shown that there is a systematic trifluoromethyl effect on X‐ray absorption that blue shifts the resonant Cu K‐edge energy by 2–3 eV per CF3, completely accounting for observed changes in DAFS profiles between formally Cu(III) complexes like 1 and formally Cu(I) complexes like (Ph3P)3CuCF3 (3). Thus, in agreement with the inverted ligand field model, the data presented herein imply that 1 is best described as containing a Cu(I) ion with dn count approaching 10.

Metal Site-Specific Electrostatic Field Effects on a Tricopper(I) Cluster Probed by Resonant Diffraction Anomalous Fine Structure (DAFS).

Studies of multinuclear metal complexes are greatly enhanced by resonant diffraction measurements, which probe X-ray absorption profiles of crystallographically independent metal sites within a cluster. In particular, X-ray diffraction anomalous fine structure (DAFS) analysis provides data that can be interpreted akin to site-specific XANES, allowing for differences in metal K-edge resonances to be deconvoluted even for different metal sites within a homometallic system. Despite the prevalence of Cu-containing clusters in biology and energy science, DAFS has yet to be used to analyze multicopper complexes of any type until now. Here, we report an evaluation of trends using a series of strategically chosen Cu(I) and Cu(II) complexes to determine how energy dependencies of anomalous scattering factors are impacted by coordination geometry, ligand shell, cluster nuclearity, and oxidation state. This calibration data is used to analyze a formally tricopper(I) complex that was found by DAFS to be site-differentiated due to the unsymmetrical influence on different Cu sites of the electrostatic field from a proximal K+ cation.

Unravelling the local crystallographic structure of ferromagnetic gamma '-hbox {Ga}_y hbox {Fe}_{4-y}N nanocrystals embedded in GaN

In the Fe-doped GaN phase-separated magnetic semiconductor Gadelta FeN, the presence of embedded gamma '-hbox {Ga}_y hbox {Fe}_{4-y}N nanocrystals determines the magnetic properties of the system. Here, through a combination of anomalous X-ray diffraction and diffraction anomalous fine structure, the local structure of Ga in self-assembled face-centered cubic (fcc) gamma '-hbox {Ga}_y hbox {Fe}_{4-y}N nanocrystals embedded in wurtzite GaN thin layers is investigated in order to shed light onto the correlation between fabrication parameters, local structural arrangement and overall magnetic properties of the material system. It is found, that by adjusting the growth parameters and thus, the crystallographic surroundings, the Ga atoms can be induced to incorporate into 3c positions at the faces of the fcc crystal lattice, reaching a maximum occupancy of 30%. The magnetic response of the embedded nanocrystals is ferromagnetic with Curie temperature increasing from 450 to 500 K with the Ga occupation. These results demonstrate the outstanding potential of the employed experimental protocol for unravelling the local structure of magnetic multi-phase systems, even when embedded in a matrix containing the same element under investigation.

Nanoscale x-ray investigation of composition fluctuations in AlGaN nanowires

In the present study we combined, in the same synchrotron x-ray experiment, reciprocal space mapping, multiwavelength anomalous diffraction and diffraction anomalous fine structure, to determine the strain, crystallographic polarity, alloy composition and ordering at the atomic scale in [0001]-oriented AlGaN nanowires grown by molecular beam epitaxy on GaN nanowire bases. The information that we obtained was averaged over a macroscopic ensemble of NWs. We found from the diffraction anomalous fine structure that there were an isotropic increased number of Ga-Ga pairs in the Ga next nearest coordination shell (cation sublattice) with respect to what is expected for the AlGaN alloy composition determined by anomalous diffraction. This significant deviation from random alloy atomic distribution is present whatever the AlN molar fraction and growth conditions. Our results are consistent with nanoscale composition fluctuations expected from both alloy disorder or kinematically driven spontaneous ordering, both effects being suspected to account for the physical properties of AlGaN ternary alloys.

Local structure investigation of cobalt ferrite-based nanoparticles by synchrotron X-ray diffraction and absorption spectroscopy

In this work, the local structure of ferrite nanoparticles (CoFe2O4) composed of a cobalt ferrite core surrounded by a thin layer of maghemite (CoFe2O4@γ-Fe2O3) was investigated by crossing analyses of X-ray powder Diffraction (XRD), X-ray Absorption Spectroscopy (XANES/EXAFS) and Diffraction Anomalous Fine Structure (DAFS). The proportion of the core and the shell phases was carefully checked by chemical analysis. The whole of these multiple complementary techniques confirmed the non-equilibrium site occupancy in the cobalt ferrite core. The cation distribution was precisely determined showing that about 15% of cobalt ions are located at tetrahedral sites. The results of EXAFS spectra indicated interatomic distances very close to bulk values. The mean coordination number of both metallic cations was found to be lower than expected for bare nanoparticles and reflected the core-shell structure in CoFe2O4@γ-Fe2O3 ones. Finally, DAFS analyses were applied to enlighten the local structure around iron atoms in specific Bragg planes.

FORTE - a multipurpose high-vacuum diffractometer for tender X-ray diffraction and spectroscopy at the SIRIUS beamline of Synchrotron SOLEIL.

A new high-vacuum multipurpose diffractometer (called FORTE from the French acronyms of the project) has recently been installed at the tender/hard X-ray SIRIUS beamline of Synchrotron SOLEIL, France. The geometry chosen allows one to work either in the classical Eulerian four-circle geometry for bulk X-ray diffraction (XRD) or in the z-axis geometry for surface XRD. The diffractometer nicely fits the characteristics of the SIRIUS beamline, optimized to work in the 1.1-4.5 keV range, and allows one to perform unprecedented diffraction anomalous fine structure (DAFS) experiments in the tender X-ray region, also around non-specular reflections, covering a large reciprocal-space volume. Installation of an X-ray fluorescence detector on a dedicated flange allows simultaneous DAFS and X-ray absorption (XAS) measurements. The access to the tender X-ray region paves the way to resonant investigations around the L-edges of second-row transition elements which are constituents of functional oxide materials. It also enables access to several edges of interest for semiconductors. Finally, the control architecture based on synchronized Delta Tau units opens up exciting perspectives for improvement of the mechanical sphere of confusion.

Gallium clustering and structural effects of hydrogenation in InGaN/GaN nanostructures

We addressed the issue of atomic ordering in a series of In-rich InxGa1−xN epilayers grown on a GaN/AlN/sapphire(0001) epitaxial template by quantitatively measuring the Ga-cation coordination in the second atomic shell of Ga. We used Diffraction Anomalous Fine Structure Spectroscopy (DAFS) at the Ga K-edge to select the signal coming from the Ga atoms in the epilayer and eliminate any contribution from the buffer layer. DAFS measurements were also performed on hydrogenated epilayers in order to investigate the possible formation of Ga-H complexes. We find that deviation from cation random distribution in the form of Ga clustering is present in both untreated and hydrogenated samples and that in the latter ones the second atomic shell around Ga is modified, suggesting an additional perturbation of the cation sublattice related to hydrogen. However, comparing the present results with In K-edge x-ray absorption spectra previously reported, we conclude that the formation of Ga-H complexes vs. In-H ones is unlikely. Cation clustering has to be anyway taken into account as a possible channel playing in the determination of the optical bandgap of these technology-oriented semiconductors.

A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K- and L-edge XANES spectral simulations and resonance photoelectron spectroscopy

X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for distinguishing each contribution of Ni, Co, Mn, and O to the redox reactions during charge operation. In addition to the XANES analysis, we applied resonant photoelectron spectroscopy (RPES) and diffraction anomalous fine structure spectroscopy (DAFS) with first-principles calculations to the reaction analysis of Co and Mn, which shows no or very little contribution to the redox. The combination of RPES and first-principles calculations successfully enables us to confirm the contribution of Co at high potential regions by electively observing Co 3d orbitals. Through the DAFS analysis, we deeply analyzed the spectral features of Mn K-edges and concluded that the observed spectral shape change for Mn does not originate from the valence change but from the change in distribution of wave functions around Mn upon Li extraction.

X-ray multi-beam resonant diffraction analysis of crystal symmetry for layered perovskite YBaCuFeO5

The open question of crystal symmetry for YBaCuFeO5, still under debate, is resolved by using diffraction anomalous fine structure and resonant multi-beam X-ray diffraction at the Fe and Cu K edges. The different asymmetric intensity distributions observed at 7, 7.1305 and 8.9945 keV give direct evidence that the space group of YBaCuFeO5 should be P4/mmm with the distance between Cu and apical O atoms longer than that between Fe and O atoms. This approach provides a direct way to resolve detailed structural symmetry which is indeterminate in conventional Bragg diffraction.

Site-Selective and Element-Selective Analysis of Nickel Substituted Li-Rich Layered Material Using By X-Ray Diffraction and Absorption Spectroscopy

1. Introduction Li-rich type (manganese) oxides are one of the most featured cathodes for lithium ion batteries in recent years, owing to their high capacity and cyclability. In these cathodes, partial substitution of manganese by other transition metals such as Ni and Co has been proposed and shown to be effective in improving the performance, [1] however, the role of such metals in the battery performance has not been clarified in detail.We have synthesized Ni ion substituted Li excess manganese oxides (Li2Mn1-xNixO3) as a simple model of Li2MeO3 phase in solid solution cathode to understand the effect of introduced Ni by using the combination of in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction spectroscopy (XDS) analysis. Diffraction anomalous fine structure (DAFS) spectra are achieved by XDS analysis, that there were quantitatively showed potential-dependent transbilayer migration of nickel and manganese and their reversibility. 2. Experimental procedure The active material of nickel substituted Li2MnO3 (Li2Mn1-x NixO3, x = 0 ~ 0.25) was prepared from solid phase calcination at 1173 K for 12 h in air. The working electrode consisted of active material (80 wt.%), acetylene black (10 wt.%) and polyvinylidene difluoride (PVdF) binder (10 wt.%), coated on aluminum current foil.The electrochemical measurements of the electrode were employed using aluminum pouch type cells, metallic lithium as counter and reference electrodes, 1 mol dm-3 LiPF6 in a 3:7 mixture of EC/DMC, and a polyolefin film as a separator. The electrochemical charge and discharge tests were performed at room temperature and the potential range was between 2.0 and 4.8 V.XAS measurements were performed by the three-electrode cell with charging and discharging processes (in Operando). The XAS measurements of the Ni-K and Mn-K edge region were performed using a solid-state detector at beamlines BL28XU in SPring-8 (Hyogo, Japan).The XDS measurements were conducted at beamline BL28XU, SPring-8, Japan. A two-dimensional Pilatus detector (Dectris Co., Ltd.) was mounted onto an arm of a multi-axis goniometer and was used to measure the diffraction profile, and two ionization chamber was used for the absorption correction of the DAFS spectra. 3. Results and Discussion The obtained X-ray absorption near edge structure (XANES) region spectra at N-K energy region of Li2Mn1-x NixO3 (x = 0.25) in the 1st charging and discharging processes are shown in Fig. 1. The edge energy was shifted to high energy, which is suggested that Ni element function as a charge compensation species. However the end of charging region around 4.7 V to 4.8 V was shifted to low energy as seen in previous XAS report [2], which means the reduction of nickel on average in this region.As our group have published before,[3] XANES-like spectra only from selected sites (i.e. DAFS spectra) can be extracted from the XDS analysis. Fig. 2 shows the DAFS spectra of initial sample. The Ni-K edge XANES-like spectra shows that there was cation mixing in the lithium layer of the pristine material. In contrast, Mn-K edge XANES-like spectra shows that manganese mostly occupied in transition metal layer. XDS analysis of the fully charged sample indicated that Ni element further migrated to the lithium layer.These analytical approaches are important to understand the metal migration behavior as a function of operation potential together with the charge compensation mechanism during electrochemical charging and discharging.

Analysis of modulated Ho2PdSi3 crystal structure at Pd K and Ho L absorption edges using resonant elastic X-scattering

Replacing Si atoms with a transition metal in rare earth disilicides results in a family of intermetallic compounds with a variety of complex magnetic phase transitions. In particular, the family R2PdSi3 shows interesting magnetic behavior arising from the electronic interaction of the R element with the transition metal in the Si network, inducing the specific structure of the related phase. Within this series, the highest degree of superstructural order was reported for the investigated representative Ho2PdSi3, although several competing superstructures have been proposed in literature.The diffraction anomalous fine structure (DAFS) method is highly sensitive to the local structure of chosen atoms at specific positions within the unit cell of a crystalline phase. In combination with x-ray absorption fine structure (XAFS), this sophisticated synchrotron method has been applied in the present work to several selected reflections, i.a. a satellite reflection. Extensive electronic modeling was used to test the most relevant structure proposals. The superstructure has been strongly confirmed, although a small amount of disorder in the modulation is very probable.

The competitive growth of cubic domains in Ti(1-x)AlxN films studied by diffraction anomalous near-edge structure spectroscopy.

Titanium and aluminium nitride films deposited by magnetron sputtering generally grow as columnar domains made of oriented nanocrystallites with cubic or hexagonal symmetry depending on Al content, which are embedded in more disordered grain boundaries. The substitution of Al atoms for Ti in the cubic lattice of the films improves their resistance to wear and oxidation, allowing their use as protective coatings. Ti K-edge X-ray absorption spectroscopy, which probes both crystallized and more disordered grain boundaries, and X-ray diffraction anomalous fine structure, which is sensitive to short- and long-range order within a given crystallized domain, are carried out on a set of Ti(1-x)AlxN films deposited by magnetron sputtering on Si substrates. Attention is paid to the shape of the pre-edge region, which is sensitive to the symmetry of the site occupied by Ti atoms, either octahedral in face-centred-cubic Ti-rich (TiN, Ti0.54Al0.46N) samples or tetrahedral in hexagonal-close-packed Al-rich (Ti0.32Al0.68N) films. In order to obain information on the titanium environment in the well crystallized areas, subtraction of the smooth part of the energy-dependent structure factor for the Bragg reflections is applied to the pre-edge region of the diffraction anomalous data in order to restore their spectroscopic appearance. A flat pre-edge is related to the typical octahedral environment of Ti atoms for cubic reflections. The difference observed between pre-edge spectra associated with face-centred-cubic 200 and 111 Bragg reflections of Ti0.54Al0.46N is assigned to Ti enrichment of 111 large well ordered domains compared with the more disordered 200 ones. The sharp peak observed in the spectrum recorded from the hexagonal 002 peak of Ti0.32Al0.68N can be regarded as a standard for the pure tetrahedral Ti environment in hexagonal-close-packed nitride.

Roles of transition metals interchanging with lithium in electrode materials.

Roles of antisite transition metals interchanging with Li atoms in electrode materials of Li transition-metal complex oxides were clarified using a newly developed direct labeling method, termed powder diffraction anomalous fine structure (P-DAFS) near the Ni K-edge. We site-selectively investigated the valence states and local structures of Ni in Li0.89Ni1.11O2, where Ni atoms occupy mainly the NiO2 host-layer sites and partially the interlayer Li sites in-between the host layers, during electrochemical Li insertion/extraction in a lithium-ion battery (LIB). The site-selective X-ray near edge structure evaluated via the P-DAFS method revealed that the interlayer Ni atoms exhibited much lower electrochemical activity as compared to those at the host-layer site. Furthermore, the present analyses of site-selective extended X-ray absorption fine structure performed using the P-DAFS method indicates local structural changes around the residual Ni atoms at the interlayer space during the initial charge; it tends to gather to form rock-salt NiO-like domains around the interlayer Ni. The presence of the NiO-like domains in the interlayer space locally diminishes the interlayer distance and would yield strain energy because of the lattice mismatch, which retards the subsequent Li insertion both thermodynamically and kinetically. Such restrictions on the Li insertion inevitably make the NiO-like domains electrochemically inactive, resulting in an appreciable irreversible capacity after the initial charge but an achievement of robust linkage of neighboring NiO2 layers that tend to be dissociated without the Li occupation. The P-DAFS characterization of antisite transition metals interchanging with Li atoms complements the understanding of the detailed charge-compensation and degradation mechanisms in the electrode materials.

Revisit to diffraction anomalous fine structure.

The diffraction anomalous fine structure (DAFS) method that is a spectroscopic analysis combined with resonant X-ray diffraction enables the determination of the valence state and local structure of a selected element at a specific crystalline site and/or phase. This method has been improved by using a polycrystalline sample, channel-cut monochromator optics with an undulator synchrotron radiation source, an area detector and direct determination of resonant terms with a logarithmic dispersion relation. This study makes the DAFS method more convenient and saves a large amount of measurement time in comparison with the conventional DAFS method with a single crystal. The improved DAFS method has been applied to some model samples, Ni foil and Fe3O4 powder, to demonstrate the validity of the measurement and the analysis of the present DAFS method.

Structure Determination of Ho2PdSi3

Holmium-Palladium-Silicide Ho2PdSi3 is a member of rare earth-transition metal silicides exhibiting a wide range of interesting magnetic and electrical properties like multiple transition temperatues. The crystal structure results from HoSi2 by substitution of Si by Pd which is ordering commensurably with a 2 × 2 × 8 superstructure confirmed by a previous XRD and a Diffraction Anomalous Fine Structure (DAFS) measurement of the super structure reflection 1/2 1/2 3/8. DAFS is a X-ray method combining the advantages of absorption and diffraction and hence offers the possibility of element and site selective studies. Thus, it was feasible to probe the local environment of Ho and Pd separately. In the following, we will present a comparison of several structure proposals of Ho2PdSi3 with experimental data from beamline E2 and BW1 of the former synchrotron DORIS III at DESY/HASYLAB.

Progress and challenges in the theory and interpretation of x-ray spectra

There has been dramatic progress in recent years both in calculations and the interpretation of various x-ray spectra, ranging from extended x-ray absorption fine structure (EXAFS) and diffraction-anomalous fine structure (DAFS) to near-edge structure (XANES) and inelastic x-ray scattering (IXS). Using synchrotron radiation x- ray sources, these spectroscopies have become powerful probes of complex materials ranging from catalysts and minerals to bio-structures and aqueous systems. Together with advances in analysis techniques, these methods permit an interpretation of spectra in terms of structural, electronic, magnetic and vibrational properties. We summarize these advances first with a heuristic description of the real-space approach used in the electronic structure and spectroscopy codes developed by our group [1]. Our approach is based on real-space multiple-scattering Green's function techniques, rather than wave-functions. This simplifies calculations of excited states and x-ray spectra, particularly the inclusion of key many-body effects and relativistic corrections. The approach is illustrated with applications to various x-ray spectra of complex materials. For example, DAFS takes advantage of the fine structure in the intensity of Bragg diffraction peaks near an absorption edge, and provides unique information that combines EXAFS and XRD experiment. We also discuss some recent theoretical developments leading to a new generation of codes including FEFF9 [2] and extensions for treating strongly correlated systems.

Advanced Crystallographic Program at ChemMatCARS at Advanced Photon Source

ChemMatCARS, a state-of-the-art synchrotron-based national facility for Chemistry and Materials Science located at the Advanced Photon Source (APS), maintains dedicated advanced crystallographic programs for small molecule which include photo-crystallography, high resolution charge density studies, high pressure (<10 GPa) chemical crystallography using a diamond anvil cell(DAC), ultra-low temperature crystallography using open flow Helium at ~10 K, and element-specific resonant diffraction and diffraction anomalous fine structure (DAFS) (tunable energy from 5 to 70 keV). High throughput micro-crystallography benefits from a new sample preparation environment and a fast data collection strategy to enable measurements on air-sensitive samples in fewer than 5 minutes. This work is typically done by cooling the sample with cryogenic open flow nitrogen or helium. These new capabilities will impact the development of new materials to meet emerging challenges in energy, environment and life sciences. This poster focuses on the above scientific research activities and provides information on how to apply for beam time.

Study La0.5Sr1.5MnO4with Multi-Beam X-ray Diffraction

We have used resonant multi-beam diffraction with the primary reflections G=(h/2 h/2 0) and G=(h/4 h/4 0) (h is an odd number) to investigate the charge ordering and Jahn-Teller distortion, respectively, in La0.5Sr1.5MnO4 low temperature phase. While the Renninger scans with G=(h/2 h/2 0) shows several Aulfhellung-type four-beam diffraction, most of the multi-beam diffraction with G=(h/4 h/4 0) has an Umweganregung-type nature. A detailed study of multi-beam diffraction anomalous fine structure (M-DAFS) of (0 0 0)/(3/2 3/2 0)/(1 -1 0)/(5/2 1/2 0) OUT diffraction is carried out. Its triplet invariant phase approach 1800when the x-ray energy is tuned away from manganese K-edge, and approach 900when the x-ray energy is tuned on manganese K-edge. In other words, its multi-beam diffraction profile shows strong asymmetry when (3/2 3/2 0) diffraction intensity is dominated by Jahn-Teller distortion, and becomes more symmetric when charge ordering dominated. This characteristic can be successfully simulated by tensor form dynamical x-ray diffraction theory accompanied with FDMNES software [1] calculations.