An EPR and SQUID magnetometry study of bornite

A magnetic and spectroscopic characterisation has been performed on a natural bornite sample from the Natural History Museum of the University of Florence. The combination of magnetic measurements and continuous-wave electron paramagnetic resonance (cw-EPR) spectroscopy at different temperatures and frequencies provided information about the distribution and valence states of Cu and Fe in bornite. The studied sample was found to obey the Curie–Weiss law with a transition from a paramagnetic to an antiferromagnetic phase at 64 K; its possible attribution to a disordered spin glass phase was ruled out by ac susceptibility measurements. Q- and X-band cw-EPR measurements confirmed the presence of Fe(III) as fundamental valence state in bornite: the single EPR line registered in the temperature range from 300 to 65 K can be assigned, in fact, to the Fe(III) single ions. Some Cu(II) signals were revealed in the low temperature EPR spectra and attributed to an early stage of the surface alteration. The width of the Fe(III) EPR spectrum, which hinders any characteristic spectral structure, can be ascribed to the exchange interaction. The pure antiferromagnetic character of the magnetic transition confirms the ordering between Fe and Cu in the bornite structure, at least at low temperature (≤70 K). Moreover, the relatively high Nèel temperature suggests the accepted model of Collins et al.’s (Can J Phys 59:535–539, 1981) to conveniently explain the overall magnetic properties in the range 298–4 K. Despite the increasing of the susceptibility in the paramagnetic range, in fact, the integrated EPR line area decreases by lowering the temperature, thus suggesting a progressive rising of the antiferromagnetic interactions among next-nearest-neighbouring paramagnetic centres.     

Magnetic properties and cation ordering of nanopowders of the synthetic analogue of kuramite, Cu3SnS4

An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu₃SnS₄, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu₃SnS₄ crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)₂Cu(II)SnS₄ and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.     

EPR and SQUID magnetometry study of Cu2FeSnS4 (stannite) and Cu2ZnSnS4 (kesterite)

An EPR and SQUID magnetometry study of Cu₂FeSnS₄ (stannite) and Cu₂ZnSnS₄ (kesterite) has been performed in order to gain a deeper insight into the crystal chemistry of these minerals, in which the mixed character of bonds lends uncertainty to the determination of the metal valence states. EPR investigations were performed down to almost liquid nitrogen temperature on both natural and synthetic samples of stannite and kesterite. The interpretation of their parameters (g- and T-tensors) was refined by computer simulation. The main feature of all the spectra is the unstructured signal centered at about 0.310 T due to the presence of Cu(II). The absence of structure in the signal is due to spin-spin exchange interaction between Cu(II) and Fe(II), pointing to a diluted distribution of Cu(II). The temperature dependence of the Cu(II) signal can be related to a topological variation of the first-neighbors coordination. The SQUID measurements, while allowing a more precise interpretation of the EPR data, led to a full characterization of magnetic behavior of stannite and kesterite down to liquid helium temperature, evidencing antiferromagnetic interactions between the Fe(II) ions in all samples but in synthetic kesterite. From the EPR and SQUID experimental data no evidence was provided for the existence of two different structures for stannite and kesterite. Received: 2 August 1999 / Accepted: 7 January 2000     

Magnetic properties of sheet silicates; 2:1 layer minerals

Susceptibility, magnetisation and Mössbauer measurements are reported for a representative selection of 2:1 layer phyllosilicates. Eight samples from the mica, vermiculite and smectite groups include examples diluted in iron which are paramagnetic at all temperatures, as well as iron-rich silicates which order magnetically below 10 K. Anisotropic susceptibility of crystals of muscovite, biotite and vermiculite is quantitatively explained with a model where the Fe²⁺ ions lie in sites of effective trigonal symmetry, the trigonal axis lying normal to the sheets. The ferrous ground state is an orbital singlet. Ferric iron gives an isotropic contribution to the susceptibility. Fe²⁺-Fe²⁺ exchange interactions are ferromagnetic with y ～ 2 K, whereas Fe³⁺-Fe³⁺ coupling is antiferromagnetic in the purely ferric minerals. A positive paramagnetic Curie temperature for glauconite may be attributable to Fe²⁺ → Fe³⁺ charge transfer. Magnetic order was found to set in inhomogeneously for glauconite at 1–7 K. One biotite sample showed an antiferromagnetic transition at T _N =7 K marked by a well-defined susceptibility maximum. Its magnetic structure, consisting of ferromagnetic sheets with moments in their planes coupled antiferromagnetically by other, weak interactions, resembles that found earlier for the 1:1 mineral greenalite.     

Magnetic order in acmite; NaFeSi2O6

The magnetic properties of two samples of acmite, one natural and the other synthetic, were determined using magnetization and susceptibility measurements, Mössbauer spectroscopy and neutron diffraction. Exchange interactions are quite strongly antiferromagnetic, the paramagnetic Curie temperature being -46 K for a purely ferric synthetic sample, but its Néel temperature is only 8 K. The principal magnetic mode has the periodicity of the crystallographic structure and is made of ferromagnetic chains, coupled antiferromagnetically. Moments are oriented in a direction close to the chain axis, c. The antiferromagnetic exchange between adjacent Fe³⁺ ions in the same chain is overcome by their coupling to a common Fe³⁺ neighbour in the next chain. This indicates that the whole (SiO₄) group can act as a superexchange ligand in silicates.     

Magnetic phase diagrams of Mg-, Fe-, (Cu + Ti)- and Cu-substituted braunite Mn<Superscript>2+</Superscript>Mn<Subscript>6</Subscript><Superscript>3+</Superscript>SiO<Subscript>12</Subscript>

 The magnetic behavior of the Jahn-Teller structure braunite, (Mn²⁺ _1−yM _y )(Mn³⁺ _{6− x} M_x)SiO₁₂, is strongly influenced by the incorporation of elements substituting manganese. Magnetic properties of well-defined synthetic samples were investigated in dependence on the composition. The final results are presented in magnetic phase diagrams. To derive the necessary data, ac susceptibility and magnetization of braunites with the substitutional elements M = Mg, Fe, (Cu+Ti) and Cu were measured. Whereas the antiferromagnetic ordering temperature, T _N , of pure braunite is hardly affected by the substitution of nonmagnetic Mg, it is rapidly suppressed by the substitution of magnetic atoms at the Mn positions. Typically for a concentration (x, y) ≥ 0.7 of the substituted elements, a spin glass phase occurs in the magnetic phase diagrams. Additionally, for the braunite system with Fe³⁺ substitutions, we observe in the concentration range 0.2 < x< 0.7 a double transition from the paramagnetic state, first to the antiferromagnetic state, followed by a transition to a spin glass state at lower temperatures. The unusual change of the magnetic properties with magnetic substitution at the Mn positions is attributed to the peculiar antiferromagnetic structure of braunite, which has been resolved recently. Received: 19 April 2001 / Accepted: 6 September 2001     

Copper valence,structural separation and lattice dynamics in tennantite (fahlore): NMR,NQR and SQUID studies

Electronic and magnetic properties of tennantite subfamily of tetrahedrite-group minerals have been studied by copper nuclear quadrupole resonance (NQR), nuclear magnetic resonance (NMR) and SQUID magnetometry methods. The temperature dependences of copper NQR frequencies and line-width, nuclear spin-lattice relaxation rate T ₁⁻¹ and nuclear spin-echo decay rate T ₂⁻¹ in tennantite samples in the temperature range 4.2–210 K is evidence of the presence of field fluctuations caused by electronic spins hopping between copper CuS₃ positions via S₂ bridging atom. The analysis of copper NQR data at low temperatures points to the magnetic phase transition near 65 K. The magnetic susceptibility in the range 2–300 K shows a Curie–Weiss behavior, which is mainly determined by Fe²⁺ paramagnetic substituting ions.     

Magnetic properties of oxidized and reduced smectites

 Four smectites with different total Fe contents (two nontronites, one ferruginous smectite, and one montmorillonite) were reduced to obtain a range of Fe(II)/Fe(III) ratios and their magnetic properties measured with a SQUID (superconducting quantum interference device) as a function of applied magnetic field strength at 5 K and as a function of temperature in a field of 0.1 T. The unaltered nontronite and ferruginous smectite specimens showed antiferromagnetic coupling, whereas the coupling in the reduced samples was ferromagnetic; the paramagnetic Curie temperature increased with increasing Fe(II) content. Data collected after cooling samples in both the presence and absence of an external magnetic field of 0.1 T showed that at low temperatures the reduced (ferromagnetic) nontronite and ferruginous smectite samples exhibit a memory effect of previous magnetic field exposure consistent with superparamagnetic or spin glass behavior. The superparamagnetic/ferromagnetic transition temperature, T _f , increased linearly with increasing Fe(II) content for each of the nontronites, but the relationship between T _f and Fe(II) content differed for different clays, thus demonstrating that T _f is sensitive to isomorphous substitutions in the clay structure. The montmorillonite was paramagnetic in both oxidized and reduced forms. Received: 23 March 1999 / Revised, accepted: 27 August 1999     

The unusual magnetic properties of kuramite–stannite pseudobinary series: a SQUID and EPR survey

The magnetic properties of the synthetic Cu₃SnS₄ (kuramite)–Cu₂FeSnS₄ (stannite) pseudobinary series were investigated by means of electron paramagnetic resonance (EPR) spectroscopy, at room temperature, and by magnetometry, in the range 2–300 K. The system is particularly complex, from both chemical and crystal chemical points of view, in particular with respect to the metal valence states and the local ordering in the different terms of the series. Nevertheless, recent successes in synthesising nanostructured kuramite foster the interest to ascertain the bulk magnetic properties of these important semiconducting phases. The obtained results allowed to ascertain that a variable lack of local ordering in the Cu_3–x Fe _x SnS₄ (x < 0.85) samples induce the raise of strong metal–sulphur–metal superexchange interactions, that result in the appearance of marked deviations from the single-ion behaviour, typical for pure stannite. Ferro- and antiferromagnetic interactions are in fact observed at relatively high temperatures (~150 K). A possible role played by Cu(I)–Fe(III) was revealed by the EPR measurements. The Cu-rich terms of the series (x < 0.1) are characterised by dynamic resonant disorder (i.e. time-evolving delocalisation of the formally divalent valence state for Cu among the nearest neighbouring Cu-sites), in addition to the Cu–Fe–Sn static disorder verified along the whole series. Both factors concurring to a non-periodic arrangement of paramagnetic ions in the lattice have the main effect to drastically broaden the EPR lines.     

Characterisation of the antiferromagnetic transition of Cu<Subscript>2</Subscript>FeSnS<Subscript>4</Subscript>, the synthetic analogue of stannite

Magnetisation measurements were performed on the synthetic analogue of stannite, Cu₂FeSnS₄, in order to characterise the antiferromagnetic transition at low temperature, evidenced by Bernardini et al. (2000). Temperature and field dependence of the material were checked by means of static magnetisation measurements, carried out scanning the magnetic fields up to 12 T and temperatures in the range 1.4–20 K, while ac susceptibility data were collected at different frequencies ranging from 1.8 to 510 Hz. Both static and dynamic magnetisation data, performed above and below the Néel temperature, 6.1(2) K, confirm stannite to order antiferromagnetically at a long-range scale. Moreover, an increase of both the magnetic anisotropy and the exchange interaction, with respect to the Mn-analogue (Fries et al. 1997), has been observed.     

An easy and fast IC-CL procedure for the monitoring of Cu(II) and Co(II) in environmental samples

A luminol chemiluminescence (CL) detection/flow injection analysis technique coupled with ion chromatography (IC) has been employed for the determination of low levels of Cu(II) and Co(II) in drinking water samples. The detection system was the CL of luminol/perborate or luminol/percarbonate in alkaline medium catalyzed by these transition metals. Oxalic acid in a solution of KOH and N(CH₃)₄OH was used as an eluent in the IC to improve the column selectivity (Dionex CS5A). Concentration and pH of the eluent affected simultaneously the CL intensity and the retention times (t _R). Under the elution conditions used here, the retention times of both metal ions were much greater when the concentration of oxalic acid was decreased. Thus, R _t(_Cu) = 2.15 min and t _R(_Co) = 4.50 min were measured at 80 mM oxalic acid concentration, while t _R raised to 4.12 and 18 min for Cu(II) and Co(II), respectively, using a 10-mM concentration, but on the other hand, the CL signals showed substantially higher values when the concentration of oxalic acid was lesser in the eluent. An optimum oxalic acid concentration of 20 mM and an eluent pH = 4.7 were selected in order to have reproducible signals with a total analysis time of 10 min. The optimum flow rate for the mobile phase was 1.5 mL min^?1. The concentration and pH of the postcolumn reagents also affected the CL signal, obtaining optimum concentrations of 5 mM for both oxidants (perborate or percarbonate) and luminol, this last dissolved in a 0.1-M borate buffer at pH 12. The optimum flow rate for the postcolumn reagents was 1 mL min^?1. Linear calibrations for both transition metal ions were established, with calculated detection limits of 0.15 ng mL^?1 for Co(II) and 0.20 μg mL^?1 for Cu(II). Others ions commonly present in natural waters showed little or no interference. The method was successfully applied to water samples spiked with Cu(II) and Co(II), obtaining recoveries in the range of 85–128%, depending on the metal concentrations.     

Electron delocalization and magnetic behavior in a single crystal of ilvaite,a mixed valence iron silicate

Ilvaite, Ca(Fe²⁺, Fe³⁺)Fe²⁺Si₂O₈(OH), a black mixed valence iron silicate shows considerable Fe²⁺?Fe³⁺ electron delocalization above 400 K, reminiscent of magnetite. A crystallographic phase transition from orthorhombic (Pnam) to monoclinic (P2 ₁/a) symmetry takes place on cooling at 343 K induced by electron ordering. In both phases, Fe²⁺ and Fe³⁺ occur in double octahedral chains parallel to the c axis. The thermal characteristics of the magnetic susceptibilities and their anisotropies in different crystallographic planes have been measured in the temperature range 400?21 K. Below 343±1K, a continuous rotation of the molar susceptibility K _∥ in the ab plane down to 90±2 K is observed, where the symmetry of the magnetic ellipsoid remains unchanged. X _a, X _b and X _c increase abruptly below 123±0.5 K, although antiferromagnetic ordering of Fe²⁺ and Fe³⁺ spins on A sites was suggested in previous Mössbauer and neutron powder diffraction studies. In addition, 1/X _a shows an antiferromagnetic maximum at 50±3 K, whereas 1/X _b and 1/X _c at first increase sharply below 123 K, followed by antiferromagnetic curvatures in the lowest temperature region. This behavior is consistent with the antiferromagnetic ordering of Fe²⁺ spins in the B sites. The observed magnetic phenomena suggest charge delocatization effects between adjacent Fe²⁺(A)-Fe³⁺(A) pairs not only along c, but also along a and b directions. The negative sign of the molar anisotropy (K _∥-K_⊥) suggests a singlet ground State ⁵A₁ for the Fe²⁺ ions, in agreement with previous Mössbauer studies.     

Mössbauer and high field magnetization studies of the solid solution CoFexAl2-xO4

By means of paramagnetic Mössbauer spectra the cation distribution of the solid solution CoFe _x Al_2?x O₄ with 0≦x≦1.5 has been determined. The existence of high field magnetic susceptibility at low temperature for samples with x≧0.4 has been interpreted in terms of non-collinear ferrimagnetic arrangements. Below the Neel temperature the spinel CoAl₂O₄ has a complex antiferromagnetic behavior.     

Structure and Mössbauer spectroscopy of barbosalite Fe2+Fe3+ 2 (PO4)2(OH)2 between 80 K and 300 K

Natural barbosalite Fe²⁺Fe³⁺ ₂ (PO₄)₂(OH)₂ from Bull Moose Mine, South Dakota, U.S.A., having ideal composition, was investigated with single crystal X-ray diffraction techniques, Mössbauer spectroscopy and SQUID magnetometry to redetermine crystal structure, valence state of iron and evolution of ⁵⁷Fe Mössbauer parameter and to propose the magnetic structure at low temperatures. At 298?K the title compound is monoclinic, space group P2₁/n, a _o ?= 7.3294(16)?Å, b _o ?=?7.4921(17)?Å, c _o ?=?7.4148 (18)?Å, β?=?118.43(3)°, Z?=?2. No crystallographic phase transition was observed between 298?K and 110?K. Slight discontinuities in the temperature dependence of lattice parameters and bond angles in the range between 150?K and 180?K are ascribed to the magnetic phase transition of the title compound. At 298?K the Mössbauer spectrum of the barbosalite shows two paramagnetic components, typical for Fe²⁺ and Fe³⁺ in octahedral coordination; the area ratio Fe³⁺/Fe²⁺ is exactly two, corresponding to the ideal value. Both the Fe²⁺ and the Fe³⁺ sublattice order magnetically below 173?K and exhibit a fully developed magnetic pattern at 160?K. The electric field gradient at the Fe²⁺ site is distorted from axial symmetry with the direction of the magnetic field nearly perpendicular to V_zz, the main component of the electric field gradient. The temperature dependent magnetic susceptibility exhibits strong antiferromagnetic ordering within the corner-sharing Fe³⁺-chains parallel to [101], whereas ferromagnetic coupling is assumed within the face-sharing [1?1?0] and [?1?1?0] Fe³⁺-Fe²⁺-Fe³⁺ trimer, connecting the Fe³⁺-chains to each other.     

Fast ion conduction character and ionic phase-transitions in disordered crystals: the complex case of the minerals of the pearceite–polybasite group

The minerals of the pearceite–polybasite group, general formula (Ag,Cu)₁₆ M ₂S₁₁ with M = Sb, As, have been recently structurally characterized. On the whole, all the structures can be described as a regular succession of two module layers stacked along the c axis: a first module layer (labeled A), with general composition [(Ag,Cu)₆(As,Sb)₂S₇]²⁻, and a second module layer (labeled B), with general composition [Ag₉CuS₄]²⁺. In detail, in the B layer of the pearceite structure silver cations are found in various sites corresponding to the most pronounced probability density function locations of diffusion-like paths. We have shown for the first time that the observed structural disorder in the B layer is strongly related to the fast ion conduction character exhibited by these minerals. This paper reports an integrated XREF, DSC, CIS and EPMA study on all the members of the pearceite–polybasite group. DSC and conductivity measurements pointed out that the 222 members show ionic-transitions at 340 K (arsenpolybasite-222) and 350 K (polybasite-222), whereas the 221 members have transitions at lower temperature, that is, 310–330 K (arsenpolybasite-221) and 335 K (polybasite-221). For the 111 members (pearceite and antimonpearceite), the transition occurs below room temperature at 273 K. In situ single-crystal X-ray diffraction experiments showed that these minerals present the same high temperature structure and are observed at room temperature either in their high temperature (HT) fast ion conductivity form or in one of the low temperature (LT) fully ordered (222), partially ordered (221) or still disordered (111) forms, with transition temperatures slightly above or below room temperature. The pearceite–polybasite group of minerals can be considered as a homogeneous series with the same aristotype, fast ion conducting form at high temperature. Depending upon the Cu content, an ordering occurs with transition temperatures related to that content: the lower the Cu content, the higher the transition temperature from the fast ion conducting HT form to the non-ion conducting form.Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Studies on the flotation of sulphides. I. The effect of Cu(II) ions on the flotation of zinc sulphide

The effect of Cu(II) ions on the froth flotation of ZnS in the absence of any collector has been studied in a Fuerstenau microflotation cell. The flotation of pure synthetic ZnS, in both cubic and hexagonal modifications, can be greatly enhanced by the adsorption of traces of Cu(II) ions. In the case of cubic ZnS, the “activating” effect of Cu(II): (a) involves the stoichiometric replacement of one Zn(II) ion in the lattice by one Cu(II) ion from solution at a rate which is independent of pH (1–5); (b) is noticeable at coverages corresponding to as little as 0.1% of a monolayer, reaches a maximum at coverages of 2–100% of a monolayer, and decreases again at higher coverages; (c) is unaffected by the presence or absence of O₂, by variation of the pH of flotation (6–10), by heating in vacuum at 250°C for two hours or by storing in the dry state for over one year; and (d) does not appear to involve any significant change in surface area or in the state of aggregation of the particles.     

Magnetic properties of the clinopyroxenes aegirine and hedenbergite: a magnetic susceptibility study on single crystals

Two natural clinopyroxene single crystals were investigated, an aegirine-augite (AEG) and a magnesian hedenbergite (HED). Both samples were carefully characterized by electron microprobe, X-ray diffraction, and Mössbauer spectroscopy. Magnetic susceptibility measurements of powdered samples reveal low temperature antiferromagnetic coupling and Curie-Weiss behaviour with T _N =7.5(5)?K, Θ _P =?19(1)?K for AEG, and T _N =31(1)?K, Θ _P =+21(1)?K for HED, respectively. Low temperature Mössbauer spectra exhibit relaxation phenomena. Magnetic susceptibility measurements of the single crystals show the direction of the magnetic moments to be lying within the a/c plane for both samples: 50(±2)° from a and 57(±2)° from c in AEG, and 45(±2)° from a and 60(±2)° from c in HED, respectively. The antiferromagnetic interchain interaction competes with the ferromagnetic intrachain interaction in both pyroxenes. In the magnesian hedenbergite a field induced magnetic transition is found. Its dependence on temperature, magnetic field and crystallographic direction is investigated and described.     

Magnetic properties of sheet silicates; 2:1:1 layer minerals

Magnetization, susceptibility and Mössbauer spectra are reported for representative chlorite samples with differing iron content. The anisotropy of the susceptibility and magnetization of a clinochlore crystal is explained using the trigonal effective crystal-field model developed earlier for 1:1 and 2:1 layer silicates, with a splitting of theT _2g triplet of 1,120K. Predominant exchange interactions in the iron-rich samples are ferromagnetic withJ=1.2 K, as for other trioctahedral ferrous minerals. A peak in the susceptibility of thuringite occurs atT _m=5.5 K, and magnetic hyperfine splitting appears at lower temperatures in the Mössbauer spectrum. However neutron diffraction reveals no long-range magnetic order in thuringite (or biotite, which behaves similarly). The only magnetic contribution to the diffraction pattern at 1.6 K is increased small angle scattering (q<0.4 Å^?1). A factor favouring this random ferromagnetic ground state over the planar antiferromagnetic state of greenalite and minnesotaite is the presence of pairs of ferric ions on adjacent sites, in conjunction with magnetic vacancies in the octahedral sheets. Monte Carlo simulations of the magnetic ground state of the sheets illustrate how long range ferromagnetic order may be destroyed by vortices forming around the Fe³⁺-Fe³⁺ pairs.     

Synthesis and magnetic properties of centennialite: a new <Emphasis Type="Italic">S</Emphasis> = ½ Kagomé antiferromagnet and comparison with herbertsmithite and kapellasite

Minerals of the atacamite group such as herbertsmithite and kapellasite have recently attracted enormous attention as the S = ½ Kagomé antiferromagnets for achieving the quantum spin liquid (QSL) state with diverse technological applications. Herein we report on the synthesis of the newly discovered mineral centennialite by using an unconventional “solid-state” reaction method at 463 K. Synthetic centennialite, Ca_1.06Cu_2.94Cl_2.01(OH)_5.99·0.73H₂O, has been characterized by scanning electron microscopy, electron microprobe analyses, Fourier-transform infrared spectroscopy, thermogravimetric and differential scanning calorimetric analyses, single-crystal X-ray diffraction structure refinements, and magnetic susceptibility measurements. The crystal structure of centennialite is characterized by a perfect (threefold symmetry) Kagomé layer with <5 % substitution between Ca and Cu and therefore differs from those of herbertsmithite and kapellasite, in which 15–25 % mixing between similar Zn and Cu atoms dramatically affects the QSL state. Centennialite remains antiferromagnetic down to ~7 K with a moderate spin frustration (i.e., a Weiss temperature θ = ?56 K and a spin frustration parameter f = 8), but exhibits a canted antiferromagnetic ordering with a ferromagnetic component at lower temperatures.     

The charge-density distribution, its multipole refinement and the antiferromagnetic structure of dioptase, Cu6[Si6O18]·6H2O

 The chemical bonding in the ring silicate mineral dioptase is investigated on the basis of accurate single-crystal X-ray diffraction data. A multipole model is used in the refinements. Static deformation electron density is mapped for the silicon tetrahedron, Cu-octahedron and water molecule in different sections. The silicon tetrahedron exhibits peaks resulting from σ-bonds between Si–sp³ hybrid orbitals and O–p orbitals. The excess density is located on bonds between the Si atom and bridge (in ring) O(1)-, O(1′)-oxygens and across the interior of the Si–O–Si angle. In the Jahn-Teller distorted Cu octahedron, in addition to peaks which result from single Cu–O σ-bonds, there are peaks which are due to 3d electrons. The analysis of crystal-field influence on the Cu charge distribution is made using the tetragonal D _{4 d} approximation for the low-symmetry (C1) Cu octahedron. The calculation of the occupancies of the 3d atomic orbitals shows that the Cu non-bonding orbitals are most populated (˜20%) and the bonding orbitals least populated (14%), as is typical for the Jahn-Teller octahedron. The effective atomic charge on the Cu atom in dioptase determined from the multipoles is +1.23e: closer to the Cu⁺¹ than to the Cu⁺² state. The charge on the Si atom has a value +1.17e, which is in the range typical for Si atoms already determined by this method. The accumulation of density on bridge oxygens and across the interior of the Si–O–Si angle may be explained by additional strain in the bond with the decrease of the Si–O–Si angle in dioptase to 132°. The same effect was found earlier in coesite. A single-crystal neutron diffraction study shows that dioptase becomes antiferromagnetic below a Néel temperature of 15.9(1) K, in contrast to the previously reported specific heat anomaly at 21 K. The magnetic propagation vector is (0, 0, 3/2) on the hexagonal triple cell or (1/2, 1/2, 1/2) in rhombohedral indices. The relation between the antiferromagnetic and the charge-density models for dioptase is discussed. The less occupied Cu d _x2−y2 orbitals are responsible for the magnetic properties. These lie in the Cu–O squares, which are approximately perpendicular to c _hex, but which are alternately inclined to it by a small angle. The magnetic moments of 0.59(1)μ _B on the Cu ions in the same level are ordered ferromagnetically, but between ions in alternate levels the coupling is antiferromagnet. Within experimental error the magnetic moments are perpendicular to the square planes, which make an angle ±13(3)° to the triad axis. Received: 8 June 2001 / Accepted: 10 January 2002