Mössbauer spectroscopy in the investigation of new mineral–related materials

New materials based on the composition of the mineral schafarzikite, FeSb $_{2}\textit {O}_{4}$ , have been synthesised. $^{57}$ Fe- and $^{121}$ Sb- Mössbauer spectroscopy shows that iron is present as Fe $^{2+}$ and that antimony is present as Sb $^{3+}$ . The presence of Pb $^{2+}$ on the antimony sites in materials of composition FeSb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ induces partial oxidation of Fe $^{2+}_{}$ to Fe $^{3+}$ . The quasi-one-dimensional magnetic structure of schafarzikite is retained in FeSb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ and gives rise to weakly coupled non-magnetic Fe $^{2+}$ ions coexisting with Fe $^{3+}$ ions in a magnetically ordered state. A similar model can be applied to account for the spectra recorded from the compound Co $_{0.5}$ Fe $_{0.5}$ Sb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ .     

Structure of some FeII − III hydroxysalt green rusts (carbonate, oxalate, methanoate) from Mössbauer spectroscopy

The abundances of Fe^II and Fe^III environments within green rusts one, GR1s, that intercalate carbonate, oxalate and methanoate (formate) anions are found from Mössbauer spectra for compositions corresponding to [Fe $^{\rm II}_{6}$ Fe $^{\rm III}_{2}$ (OH)₁₆]^2?+??[CO $_{3}^{2-}$ ?5H₂O]^2???, [Fe $^{\rm II}_{4}$ Fe $^{\rm III}_{2}$ (OH)₁₂]^2?+??[CO $_{3}^{2-}$ ?3H₂O]^2???, [Fe $^{\rm II}_{6}$ Fe $^{\rm III}_{2}$ (OH)₁₆]^2?+??[C₂O $_{4}^{2-}$ ?4H₂O]^2??? and [Fe $^{\rm II}_{5}$ Fe $^{\rm III}_{2}$ (OH)₁₄]^2?+??[2HCOO^????3H₂O]^2???. These formulae correspond to orders α, β and γ where cation distances are (2 × a ₀), ( $\surd 3$ × a ₀) or a mixture of both leading to (7 × a ₀), where ratio x = {[Fe^III]/[Fe_total]} = 1/4, 1/3 and 2/7, respectively. Anion distributions within interlayers are also devised and long-range orders determined accordingly.     

Influence of temperature on the electric,dielectric and AC conductivity properties of nano-crystalline zinc substituted cobalt ferrite synthesized by solution combustion technique

Cobalt–zinc nanoferrites with formulae Co $_{1-x}$ Zn $_{x}$ Fe $_{2}$ O $_{4}$ , where x = 0.0, 0.1, 0.2 and 0.3, have been synthesized by solution combustion technique. The variation of DC resistivity with temperature shows the semiconducting behavior of all nanoferrites. The dielectric properties such as dielectric constant ( $\varepsilon $ ’) and dielectric loss tangent (tan $\delta )$ are investigated as a function of temperature and frequency. Dielectric constant and loss tangent are found to be increasing with an increase in temperature while with an increase in frequency both, $\varepsilon $ ’ and tan $\delta $ , are found to be decreasing. The dielectric properties have been explained on the basis of space charge polarization according to Maxwell–Wagner’s two-layer model and the hopping of charge between Fe $^{2+}$ and Fe $^{3+}$ . Further, a very high value of dielectric constant and a low value of tan $\delta $ are the prime achievements of the present work. The AC electrical conductivity ( $\sigma _\mathrm{AC})$ is studied as a function of temperature as well as frequency and $\sigma _\mathrm{AC}$ is observed to be increasing with the increase in temperature and frequency.     

All-carbon detector with buried graphite pillars in CVD diamond

A diamond detector of 3D architecture without any metallization is developed for spectroscopy of ionizing radiation and single particles detection. The carbon electrode system was fabricated using a femtosecond infrared laser ( $\lambda $ = 1,030 nm) to induce graphitization on the surface and inside 4.0  $\times $  4.0  $\times $  0.4 mm $^{3}$ single-crystal chemical vapor deposition diamond slab, resulting in an array of 84 buried graphite pillars of 30  $\upmu $ m diameter formed orthogonally to the surface and connected by surface graphite strips. Sensitivity to ionizing radiation with $^{90}$ Sr $\upbeta $ -source has been measured for the 3D detector and high charge collection efficiency is demonstrated.     

Pyrid-2-yl and 2-CyanoPhenyl fused heterocyclic compounds as human P2X_{3} inhibitors: a combined approach based on homology modelling,docking and QSAR analysis

P2X receptors are hetero-oligomeric proteins that function as membrane ion channels and are gated by extracellular ATP. The hP2X $_{3}$ subunit is a constituent of the channels on a subset of sensory neurons involved in pain signaling, where ATP released by damaged and inflamed tissue can initiate action potentials. Hence, the inhibition of ATP-activated P2X $_{3}$ receptor is an exciting approach for the treatment of inflammatory and neuropathic pain. Recently, the crystal structures of zebrafish P2X $_{4}$ (zP2X $_{4})$ were obtained in closed, apo state (PDB ID: 3I5D) and ATP-bound, open state (PDB ID: 4DW1). These structures were used to develop a homology model of human P2X $_{3}$ (hP2X $_{3})$ in order to identify through docking studies, the binding modes of known P2X $_{3}$ inhibitors and their key active site interactions, along with a pharmacophore-based 3D-QSAR model for a series of 136 Pyrid-2-yl and 2-CyanoPhenyl fused heterocyclic compounds. These 3D-QSAR models have been developed with different combinations of training and test set divisions obtained by random separation, Jarvis–Patrick clustering, K-means clustering and sphere exclusion methods. The best predictive 3D-QSAR model resulted in training set R $^{2 }$ of 0.75, internal test set Q $^{2}$ of 0.74, Pearson-R value of 0.87 and root mean square error of 0.37. The information generated by the pharmacophore model and docking analyses using the homology model provides valuable clues to design novel potent hP2X $_{3}$ inhibitors.     

Analysis of the {3\over 2}^{+} heavy and doubly heavy baryon states with QCD sum rules

In this article, we study the ${3\over 2}^{+}$ heavy and doubly heavy baryon states $\varXi^{*}_{cc}$ , $\varOmega^{*}_{cc}$ , $\varXi^{*}_{bb}$ , $\varOmega^{*}_{bb}$ , $\varSigma_{c}^{*}$ , $\varXi_{c}^{*}$ , $\varOmega_{c}^{*}$ , $\varSigma_{b}^{*}$ , $\varXi_{b}^{*}$ and $\varOmega_{b}^{*}$ by subtracting the contributions from the corresponding ${3\over 2}^{-}$ heavy and doubly heavy baryon states with the QCD sum rules, and we make reasonable predictions for their masses.     

Analysis of the \frac{1} {2}^ - and \frac{3} {2}^ - heavy and doubly heavy baryon states with QCD sum rules

In this article, we study the $\frac{1} {2}^ -$ and $\frac{3} {2}^ -$ heavy and doubly heavy baryon states $\Sigma _Q \left( {\frac{1} {2}^ - } \right)$ , $\Xi '_Q \left( {\frac{1} {2}^ - } \right)$ , $\Omega _Q \left( {\frac{1} {2}^ - } \right)$ , $\Xi _{QQ} \left( {\frac{1} {2}^ - } \right)$ , $\Omega _{QQ} \left( {\frac{1} {2}^ - } \right)$ , $\Sigma _Q^* \left( {\frac{3} {2}^ - } \right)$ , $\Xi _Q^* \left( {\frac{3} {2}^ - } \right)$ , $\Omega _Q^* \left( {\frac{3} {2}^ - } \right)$ , $\Xi _{QQ}^* \left( {\frac{3} {2}^ - } \right)$ and $\Omega _{QQ}^* \left( {\frac{3} {2}^ - } \right)$ by subtracting the contributions from the corresponding $\frac{1} {2}^ +$ and $\frac{3} {2}^ +$ heavy and doubly heavy baryon states with the QCD sum rules in a systematic way, and make reasonable predictions for their masses.     

Formation and crystallization kinetics of Nd–Fe–B-based bulk amorphous alloy

In order to improve the glass-forming ability (GFA) of Nd–Fe–B ternary alloys to obtain fully amorphous bulk Nd–Fe–B-based alloy, the effects of Mo and Y doping on GFA of the alloys were investigated. It was found that the substitution of Mo for Fe and Y for Nd enhanced the GFA of the Nd–Y–Fe–Mo–B alloys. It was also revealed that the GFA of the samples was optimized by 4 at.% Mo doping and increased with the Y content. The fully amorphous structures were all formed in the Nd $_{6-{x}}$ Y $_{{x}}$ Fe $_{68}$ Mo $_{4}$ B $_{22}$ (x $=$ 1–5) alloy rods with 1.5 mm-diameter. After subsequent crystallization, the devitrified Nd $_{3}$ Y $_{3}$ Fe $_{68}$ Mo $_{4}$ B $_{22}$ alloy rod exhibited a uniform distribution of grains with a coercivity of 364.1 kA/m. The crystallization behavior of Nd $_{3}$ Y $_{3}$ Fe $_{68}$ Mo $_{4}$ B $_{22}$ BMG was investigated in isothermal situation. The Avrami exponent n determined by JAM plot is lower than 2.5, implying that the crystallization is mainly governed by a growth of particles with decreasing nucleation rate.     

Finite W-Superalgebras and Truncated Super Yangians

Let ${Y_{m|n}^{\ell}}$ be the super Yangian of general linear Lie superalgebra for ${\mathfrak{gl}_{m|n}}$ . Let ${e \in \mathfrak{gl}_{m\ell|n\ell}}$ be a “rectangular” nilpotent element and ${\mathcal{W}_e}$ be the finite W-superalgebra associated to e. We show that ${Y_{m|n}^{\ell}}$ is isomorphic to ${\mathcal{W}_e}$ .     

Spectroscopic properties of Ho 3 + -doped K–Sr–Al phosphate glasses

Trivalent holmium-doped K–Sr–Al phosphate glasses ( $\mathrm{P}_{2}\mathrm{O}_{5}$ – $\mathrm{K}_{2}\mathrm{O}$ –SrO– $\mathrm{Al}_{2}\mathrm{O}_{3}$ – $\mathrm{Ho}_{2}\mathrm{O}_{3}$ ) were prepared, and their spectroscopic properties have been evaluated using absorption, emission, and excitation measurements. The Judd–Ofelt theory has been used to derive spectral intensities of various absorption bands from measured absorption spectrum of 1.0 mol% $\mathrm{Ho}_{2}\mathrm{O}_{3}$ -doped K–Sr–Al phosphate glass. The Judd–Ofelt intensity parameters ( $\varOmega_{\lambda}$ , $\times10^{-20}~\mathrm{cm}^{2}$ ) have been determined of the order of $\varOmega_{2} = 11.39$ , $\varOmega_{4} = 3.59$ , and $\varOmega_{6} = 2.92$ , which in turn used to derive radiative properties such as radiative transition probability, radiative lifetime, branching ratios, etc. for excited states of $\mathrm{Ho}^{3+}$ ions. The radiative lifetimes for the ${}^{5}F_{4}$ , ${}^{5}S_{2}$ , and ${}^{5}F_{5}$ levels of $\mathrm{Ho}^{3+}$ ions are found to be 169, 296, and 317 μs, respectively. The stimulated emission cross-section for 2.05-μm emission was calculated by the McCumber theory and found to be $9.3\times10^{-2 1}~\mathrm{cm}^{2}$ . The wavelength-dependent gain coefficient with population inversion rate has been evaluated. The results obtained in the titled glasses are discussed systematically and compared with other $\mathrm{Ho}^{3+}$ -doped systems to assess the possibility for visible and infrared device applications.     

Structural evolution of nanopores and cracks as fundamental constituents of ultrashort pulse-induced nanogratings

We present an extensive study of the underlying structure of femtosecond laser-induced nanogratings in fused silica. To explore the evolution of the three-dimensional structure of the nanopores and cracks, of which the nanogratings consist, we performed small angle X-ray scattering measurements as well as focused ion beam milling and scanning electron microscopy. Our results show that cracks with dimensions of (280  $\times $  25  $\times $  380) nm $^{3}$ and nanopores with typical diameters of (30  $\times $  25  $\times $  75) nm $^{3}$ are formed independent of various illumination parameters. With increasing number of laser pulses the smaller pores fuse to larger structures. Furthermore, the data suggest a cross-sectional change of the pores from cuboidal to ellipsoidal.     

Local structure of Fe-doped In 2 O 3 films investigated by X-ray absorption fine structure spectroscopy

$(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ $(x=0.07, 0.09, 0.16, 0.22, 0.31)$ films were deposited on Si (100) substrates by RF-magnetron sputtering technique. The influence of Fe doping on the local structure of films was investigated by X-ray absorption spectroscopy (XAS) at Fe K-edge and L-edge. For the $(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ films with $x=0.07, 0.09 \mbox{ and } 0.16$ , Fe ions dissolve into $\mathrm{In}_{2}\mathrm{O}_{3}$ and substitute for $\mathrm{In}^{3+}$ sites with a mixed-valence state ( $\mathrm{Fe}^{2+}/\mathrm{Fe}^{3+}$ ) of Fe ions. However, a secondary phase of Fe metal clusters is formed in the $(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ films with $x=0.22 \mbox{ and } 0.31$ . The qualitative analyses of Fe-K edge extended X-ray absorption fine structure (EXAFS) reveal that the Fe–O bond length shortens and the corresponding Debye–Waller factor ( $\sigma^{2}$ ) increases with the increase of Fe concentration, indicating the relaxation of oxygen environment of Fe ions upon substitution. The anomalously large structural disorder and very short Fe–O distance are also observed in the films with high Fe concentration. Linear combination fittings at Fe L-edge further confirm the coexistence of $\mathrm{Fe}^{2+}$ and $\mathrm{Fe}^{3+}$ with a ratio of ${\sim}3:2$ ( $\mathrm{Fe}^{2+}: \mathrm{Fe}^{3+}$ ) for the $(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ film with $x=0.16$ . However, a significant fraction ( ${\sim}40~\mbox{at\%}$ ) of the Fe metal clusters is found in the $(\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}$ film with $x=0.31$ .     

Laser nanoablation of graphite

Experimental data on laser ablation of highly oriented pyrolitic graphite by nanosecond pulsed UV ( $\lambda =193$  nm) and green ( $\lambda =532$  nm) lasers are presented. It was found that below graphite vaporization threshold $\approx $ 1 J/cm $^{2}$ , the nanoablation regime can be realized with material removal rates as low as 10 $^{-3}$  nm/pulse. The difference between physical (vaporization) and physical–chemical (heating + oxidation) ablation regimes is discussed. Special attention is paid to the influence of laser fluence and pulse number on ablation kinetics. Possibility of laser-induced graphite surface nanostructuring has been demonstrated. Combination of tightly focused laser beam and sharp tip of scanning probe microscope was applied to improve material nanoablation.     

Large N approach to Kaon decays and mixing 28 years later: \Delta I=1/2 rule, \hat{B}_K,and \Delta M_K

We review and update our results for $K\rightarrow \pi \pi $ decays and $K^0$ – $\bar{K}^0$ mixing obtained by us in the 1980s within an analytic approximate approach based on the dual representation of QCD as a theory of weakly interacting mesons for large $N$ , where $N$ is the number of colors. In our analytic approach the Standard Model dynamics behind the enhancement of $\hbox {Re}A_0$ and suppression of $\hbox {Re}A_2$ , the so-called $\Delta I=1/2$ rule for $K\rightarrow \pi \pi $ decays, has a simple structure: the usual octet enhancement through the long but slow quark–gluon renormalization group evolution down to the scales $\mathcal{O}(1\, {\hbox { GeV}})$ is continued as a short but fast meson evolution down to zero momentum scales at which the factorization of hadronic matrix elements is at work. The inclusion of lowest-lying vector meson contributions in addition to the pseudoscalar ones and of Wilson coefficients in a momentum scheme improves significantly the matching between quark–gluon and meson evolutions. In particular, the anomalous dimension matrix governing the meson evolution exhibits the structure of the known anomalous dimension matrix in the quark–gluon evolution. While this physical picture did not yet emerge from lattice simulations, the recent results on $\hbox {Re}A_2$ and $\hbox {Re}A_0$ from the RBC-UKQCD collaboration give support for its correctness. In particular, the signs of the two main contractions found numerically by these authors follow uniquely from our analytic approach. Though the current–current operators dominate the $\Delta I=1/2$ rule, working with matching scales $\mathcal{O}(1 \, {\hbox { GeV}})$ we find that the presence of QCD-penguin operator $Q_6$ is required to obtain satisfactory result for $\hbox {Re}A_0$ . At NLO in $1/N$ we obtain $R=\hbox {Re}A_0/\hbox {Re}A_2= 16.0\pm 1.5$ which amounts to an order of magnitude enhancement over the strict large $N$ limit value $\sqrt{2}$ . We also update our results for the parameter $\hat{B}_K$ , finding $\hat{B}_K=0.73\pm 0.02$ . The smallness of $1/N$ corrections to the large $N$ value $\hat{B}_K=3/4$ results within our approach from an approximate cancelation between pseudoscalar and vector meson one-loop contributions. We also summarize the status of $\Delta M_K$ in this approach.     

Waveguide laser modelling of Erbium/Ytterbium activated monoclinic double tungstates

Using the overlapping integral method, a rib waveguide laser of monoclinic potassium double tungstate, KRE $(\text{ WO}_{4})_{2}$ , co-doped with Erbium and Ytterbium has been modelled. The laser operation at 1.5 $\upmu $ m is based on an efficient pump scheme via the energy transfer from Yb $^{3+}$ to Er $^{3+}$ ions. The numerical simulation requires spectroscopic parameters of the ions involved and the waveguide geometry and index profiles. This model allows determining the laser power as a function of controllable parameters such as ions doping level, pump power, cavity length or reflectance of the input/output mirrors. It has been found that, for the standard doping level used in this matrix, the optimum cavity length is only few millimeters. Overall, using simulation tools is possible to optimize fabrication parameters, and thus saving effort in the development of experimental prototypes.     

{\boldsymbol N}\boldsymbol{\bar N} exotics and antiprotonic atoms

The BES Collaboration measurements of J/ψ radiative decays into $ p{\bar p}$ indicate a strong enhancement at $ p {\bar p}$ threshold. In a related experiment a peak in the invariant π ^?+? π ^???η′ mass is observed. It is shown that both structures may be related to a broad $ N{\bar N}$ quasi-bound state in the $^{11}S_{0} $ wave. The existence of this state finds additional support from the antiprotonic atom level widths. It is also explained by a traditional model of $ N \bar{N} $ interactions based on G-parity transformation. The level widths in H, D and He antiprotonic atoms and the radiochemical studies of $ {\bar p}$ capture in nuclei indicate the existence of another near-threshold quasi-bound state in a P wave.     

Dye-sensitized solar cells with PVA–KI–EC–PC gel electrolytes

Gel polymer electrolytes consisting of PVA–EC–PC–KI have been studied in this work. The highest room temperature (298 K) conductivity of 12.92 mS cm $^{-1}$ is obtained for PVA-based gel polymer electrolyte (GPE) with composition 14.5 PVA-21.7 EC-28.7 PC-30.4 KI-4.7 $\text{ I }_{2}$ (in wt%). The high conductivity is due to the highest number density of mobile ions in the electrolyte. The conductivity–temperature dependence follows the Vogel–Tamman–Fulcher (VTF) relationship. The trend of pseudoactivation energy $(E_{a})$ with salt concentration is contrary to that of conductivity. PVA-based GPEs with 5 to 35 wt% KI were used as a medium in ruthenium 535 (N719) dye-sensitized solar cells. The efficiency ( $\eta $ ) of the solar cells increased as the composition of KI salt in the electrolyte increased. The highest power conversion efficiency of 2.74 % is obtained for solar cells fabricated with electrolyte containing 35 wt% KI. The variation of efficiency follows the same trend as short circuit current density $(J_{sc})$ . The increase in $J_{sc}$ is influenced by the increase in iodide ion concentration in the electrolyte that assists the redox process and helps electron to shuttle between ionized dye and counter electrode.     

Resonant cavity enhanced quantum ring photodetector at 20\,\upmu m wavelength

In this paper, in order to enhance the performance characteristics of photodetector, an InAs/GaAs quantum ring infrared photodetector (QRIP) with resonant cavity structure is proposed. For this purpose, distributed bragg reflectors (DBR) in the bottom of structure are used to reflect the transmitted beam back into the active region. For further confinement of light in the active region, a gold layer is added to structure as top reflector and the performance of structures is compared with and without top reflector. Numerical simulation results show that using resonant cavity structure can improve quantum efficiency and responsivity of photodetector. Furthermore, the specific detectivity of device can increase about one order of magnitude using resonant cavity structure. Results show specific detectivity, $\hbox {D}^{*}$ , about $\sim $ 10 $^{11}\,(\hbox {cm}\,\hbox {Hz}^{1/2}\hbox {/W})$ for conventional QRIP and $\sim $ 10 $^{12}\,(\hbox {cm}\,\hbox {Hz}^{1/2}\hbox {/W})$ for conventional QRIP embedded in resonant cavity. As a result of enhancement in detectivity, the operation temperature of detector can be increased up to about 150 K.     

Quasi solid state dye-sensitized solar cells based on polyvinyl alcohol (PVA) electrolytes containing \mathbf{I}^{\mathbf{-}}/\mathbf{I}_{\mathbf{3}}^{\mathbf{-}} redox couple

Quasi solid state dye-sensitized solar cells (DSSCs) have been fabricated with electrolytes containing $\text{ I }^{-}/\text{ I }_{3}^{-}$ redox couple using 80 % hydrolyzed polyvinyl alcohol (PVA) doped with potassium iodide (KI) and a mixture of potassium iodide and tetrapropyl ammonium iodide ( $\text{ Pr }_{4}\text{ NI }$ ) salts. The quasi solid state gel polymer electrolytes were prepared using 1:1 ethylene carbonate (EC):propylene carbonate (PC) mixture. The solar cells have the structure of ITO/ $\text{ TiO }_{2}$ /N3-Dye/electrolyte/Pt/ITO. The conductivity of the electrolytes has been calculated from the bulk resistance value determined using the electrochemical impedance spectroscopy. The performance of the DSSCs has been studied by varying the concentration of the doping salts in the electrolyte and incident light intensity. The DSSC fabricated with the KI salt electrolyte containing 9.9 wt% PVA, 39.6 wt% EC, 39.6 wt% PC, 10.9 wt% KI $(+\text{ I }_{2})$ exhibited the best power conversion efficiency of 1.97 %. However, the DSSC with a double-salt electrolyte containing 9.9 wt% PVA: 39.6 wt% EC: 39.6 wt% PC: (6.5 wt% KI: 4.4 wt% $\text{ Pr }_{4}\text{ NI }$ ) ( $+\text{ I }_{2}$ ) exhibited a higher efficiency of 3.27% under $100 \text{ mW/cm }^{2}$ light intensity. The efficiency of this cell increased to 4.59 % under dimmer light of intensity of $54 \text{ mW/cm }^{2}$ .     

Mössbauer study of magnetism in FeII − III (oxy-)hydroxycarbonate green rusts; ferrimagnetism of FeII − III hydroxycarbonate

Fe^II???III hydroxycarbonate Fe $^{\rm II}_{4}$ Fe $^{\rm III}_{2}$ (OH)₁₂CO₃, green rust GR(CO $_{3}^{2-})$ , reveals a ferrimagnetic behaviour. Moments that lie within two-dimensional cation layers are parallel for same species and antiparallel between Fe^II and Fe^III. Respective ordering temperatures are 5.2 and 7 K. A sextet with distribution from 350 to 580 kOe for Fe^III and an octet reflecting a mixture of states with field of 130 kOe and quadrupole splitting of ?3.0 mm s^???1 for Fe^II are observed at 1.4 K. Ferric oxyhydroxycarbonate Fe $^{\rm III}_{6}$ O₁₂H₈CO₃ is ferromagnetic and displays at 4 K a sextet with field between 400 and 500 kOe (maximum at 480 kOe) and transition at 80 K. GR(CO $_{3}^{2-})$ deprotonation gives magnetic domains with compositions at x?=?1/3, 2/3 and 1 due to long range order.