Soft mode behavior in RbH2AsO4

The low frequency xy Raman spectra of RbH₂AsO₄ are reported as a function of temperature in the paraelectric phase and are fitted to a coupled damped harmonic oscillator model to yield the soft mode behavior of the ferroelectric model.     

Paramagnetic resonance of the (Cr5+O4)H2 Halperin-Varma center in NH4H2AsO4 and KH2AsO4

The electron paramagnetic resonance (EPR) spectrum of Cr⁵⁺(3d ¹,S=1/2) in undeuterated and 58%-deuterated NH₄H₂AsO₄ was investigated. The EPRg-value tensors in the paraelectric and antiferroelectric phases are almost the same as those observed at high and low temperatures in KH₂PO₄ and KH₂AsO₄. This shows that the (Cr⁵⁺O₄)H₂ complex is the same in all crystals, i.e., a wave function ofd _x ²–y ² character coupled to two lateral protons which reorient among the four possible Slater configurations in the paraelectric phase. The remarkable isotope shift of the local dynamic reorientational slowing-down observed in KH₂PO₄ and KH₂AsO₄ in approximate proportion to the shift of the bulk ferroelectric transition temperaturesT _c ^F , and the antiferroelectricT _c ^AF of NH₄H₂AsO₄, is analyzed qualitatively. It is shown to result mainly from the isotope effect of the short-range interactionJ _sr via protons and deuterons for the impurity and for the bulk. Q-band data of the (Cr⁵⁺O₄)H₂ center in 75%-deuterated KH₂AsO₄ are also reported. An averaged high- and nonaveraged low-temperature EPR spectrum is observed in a temperature range of 250 to 290 K. The intensity ratio of the two follows an exp 2(T—T)/ law over four orders of magnitude atT=266 to 273 K and=5.3 to 6.1 K depending on the orientation of the external magnetic field. This novel result in motional narrowing is analyzed analytically to be compatible with a distributionP _A of ₀(T, T, ) of half width, in reorientation times withE=0.23 ±0.02 eV, , probably resulting from the statistical occupation of deuterium atoms among the O—–H–O bridges. Comparison with a theory of Binder definitely proves the extrinsic slowing-down and thus Halperin-Varma type character. In the range of temperatures investigated no local freeze-out has been detected.     

Electron paramagnetic resonance and electron nuclear double resonance of the AsO4 4- centre in X-irradiated KH2AsO4

Electron paramagnetic resonance studies of the AsO₄ ^4- centre in X-irradiated crystals of KH₂AsO₄ in the ferroelectric phase at 77 and 4·2 K are reported. The symmetry of the spin-hamiltonian has been found to be orthorhombic, and the g tensor and the A tensor describing the interaction of the unpaired electron with the arsenic nucleus (I = 3/2) have been obtained. Domain splitting has been observed in he spectra recorded in the ab plane of the crystal. By studying these spectra in the presence of an applied electric field, it has been possible to plot the hysteresis curve of ferroelectric KH₂AsO₄. Electron-nuclear double resonance (ENDOR) of protons surrounding the AsO₄ ^4- units has been studied at 4·2 K. Two sets of ENDOR lines have been found arising from the protons in the two equilibrium positions (labelled ‘ close ’ and ‘ far ’) along the hydrogen bonds linking the AsO₄ tetrahedra. The angular variation of the ENDOR lines from both ‘ close ’ and ‘ far ’ protons has been plotted in the crystal symmetry planes. The observed ENDOR frequencies have been fitted to those calculated from the numerical diagonalization of the Hamiltonian. The superhyperfine parameters for the ‘ close ’ and ‘ far ’ protons thus obtained are found to be quite anisotropic. The ENDOR results are shown to explain all details of the partially-resolved proton superhyperfine structure at room temperature as well as at low temperatures. An isotropic contact hyperfine coupling of -2·875 MHz of the unpaired electron to the proton in the ‘ far ’ position of the hydrogen bond has been determined, providing direct evidence for covalency in the hydrogen bonding in KH₂AsO₄ crystals.     

Hydrogen-bonded ferroelectrics: Evidence for Slater configurations from E.P.R. studies of X-irradiated KH2AsO4 and NH4H2AsO4

The temperature dependence of the powder E.P.R. spectrum of the AsO₄ ^4- centre in x-irradiated samples of KH₂AsO₄ and NH₄H₂AsO₄ yields results which can be understood as arising from exchange processes taking place between the six configurations in the Slater model for this type of hydrogen-bonded ferroelectric and antiferroelectric. Knowing that the ⁷⁵As hyperfine parameters have rhombic symmetry in the compounds studied, it is possible to interpret certain specific features in the spectra as being associated with the Slater configurations of higher energy.     

Calculated polariton shape for the ferroelectric modes in KH2AsO4

The lineshape of the polaritons resulting from the coupled system proton-phonon in KH₂AsO₄ was calculated for several wavevectors at room temperature. The results are very sensitive to the phase of the coupling, which means that carefull polariton measurements can indicate the correct representation for the coupled system.     

On the phase transition in foreign phase inclusions in CsH2AsO4, KD2PO4, and KH2PO4 crystals

The low-frequency internal friction Q ^?1 and the shear modulus G in a paraelectric phase of CsH₂AsO₄, KD₂PO₄, and KH₂PO₄ ferroelectrics were studied using a reversed torsion pendulum method. Anomalies in the Q ^?1(T) and G(T) dependences were observed above the Curie temperatures of these crystals, at temperatures 308, 253, and 293 K, respectively. The anomalies were associated with a first-order phase transition $(\bar 42m \to mm2)$ occurring in the foreign phase inclusions.     

Raman spectroscopic study of the multi‐anion mineral dixenite CuMn2+14Fe3+(AsO3)5(SiO4)2(AsO4)(OH)6

The mixed anion mineral dixenite has been studied by Raman spectroscopy, complemented with infrared spectroscopy. The Raman spectrum of dixenite shows bands at 839 and 813 cm⁻¹ assigned to the (AsO₃)³⁻ symmetric and antisymmetric stretching modes. The most intense Raman band of dixenite is the band at 526 cm⁻¹ and is assigned to the ν₂ AsO₃³⁻ bending mode. DFT calculations enabled the calculation of the position of AsO₂²⁻ symmetric stretching mode at 839 cm⁻¹, the antisymmetric stretching mode at 813 cm⁻¹, and the deformation mode at 449 cm⁻¹. The Raman bands at 1026 and 1057 cm⁻¹ are assigned to the SiO₄²⁻ symmetric stretching vibrations and those at 1349 and 1386 cm⁻¹ to the SiO₄²⁻ antisymmetric stretching vibrations. Both Raman and infrared spectra indicate the presence of water in the structure of dixenite. This brings into question the commonly accepted formula of dixenite as CuMn²⁺₁₄Fe³⁺(AsO₃)₅(SiO₄)₂(AsO₄)(OH)₆. The formula may be better written as CuMn²⁺₁₄Fe³⁺(AsO₃)₅(SiO₄)₂(AsO₄)(OH)₆·xH₂O. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman microscopy of haidingerite Ca(AsO3OH)·H2O and brassite Mg(AsO3OH)·4H2O

Raman spectroscopy has been used to study the arsenate minerals haidingerite Ca(AsO₃OH)·H₂O and brassite Mg(AsO₃OH)·4H₂O. Intense Raman bands in the haidingerite spectrum observed at 745 and 855 cm⁻¹ are assigned to the (AsO₃OH)²⁻ν₃ antisymmetric stretching and ν₁ symmetric stretching vibrational modes. For brassite, two similarly assigned intense bands are found at 809 and 862 cm⁻¹. The observation of multiple Raman bands in the (AsO₃OH)²⁻ stretching and bending regions suggests that the arsenate tetrahedrons in the crystal structures of both minerals studied are strongly distorted. Broad Raman bands observed at 2842 cm⁻¹ for haidingerite and 3035 cm⁻¹ for brassite indicate strong hydrogen bonding of water molecules in the structure of these minerals. OH···O hydrogen‐bond lengths were calculated from the Raman spectra based on empirical relations. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the arsenite minerals leiteite ZnAs2O4, reinerite Zn3(AsO3)2 and cafarsite Ca5(Ti,Fe,Mn)7(AsO3)12·4H2O

The selected arsenite minerals leiteite, reinerite and cafarsite have been studied by Raman spectroscopy. Density functional theory (DFT) calculations enabled the position of the AsO₂²⁻ symmetric stretching mode at 839 cm⁻¹, the antisymmetric stretching mode at 813 cm⁻¹ and the deformation mode at 449 cm⁻¹ to be calculated. The Raman spectrum of leiteite shows bands at 804 and 763 cm⁻¹ assigned to the As₂O₄²⁻ symmetric and antisymmetric stretching modes. The most intense Raman band of leiteite is the band at 457 cm⁻¹ and is assigned to the ν₂ As₂O₄²⁻ bending mode. A comparison of the Raman spectrum of leiteite is made with the arsenite minerals reinerite and cafarsite. Copyright © 2009 John Wiley & Sons, Ltd.     

Proton conductivity in the layer compound H3OUO2AsO4·3H2O (HU As)

The proton conductivity in H₃OUO₂AsO₄·3H₂O (HUAs) has been measured below the transition temperature at 299 K. A consistent picture of the elementary process taking place is developed from separate electrochemical, spectroscopic and calorimetric measurements. The conductivity is proposed to occur by the “vehicle mechanism” of proton transport, i.e. the cooperative motion of H₃O⁺ and H₂O. This mechanism is compared with the Grotthuss and the simple ion hopping mechanism.     

Raman spectroscopic study of the uranyl mineral metauranospinite Ca[(UO2)(AsO4)]2·8H2O

Raman spectra of metauranospinite Ca[(UO₂)(AsO₄)]₂·8H₂O complemented with infrared spectra were studied. Observed bands were assigned to the stretching and bending vibrations of (UO₂)²⁺ and (AsO₄)³⁻ units and of water molecules. U O bond lengths in uranyl and O H···O hydrogen bond lengths were calculated from the Raman and infrared spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopy of hydrogen‐arsenate group (AsO3OH) in solid‐state compounds: cobalt mineral phase burgessite Co2(H2O)4[AsO3OH]2·H2O

Raman spectrum of burgessite, Co₂(H₂O)₄[AsO₃OH]₂· H₂O, was studied, interpreted and compared with its infrared spectrum. The stretching and bending vibrations of (AsO₃) and As‐OH units, as well as the stretching, bending and libration modes of water molecules and hydroxyl ions were assigned. The range of O H···O hydrogen bond lengths was inferred from the Raman and infrared spectra of burgessite. The presence of (AsO₃OH)²⁻ units in the crystal structure of burgessite was proved, which is in agreement with its recently solved crystal structure. Raman and infrared spectra of erythrite inferred from the RRUFF database are used for comparison. Copyright © 2010 John Wiley & Sons, Ltd.