Optical studies of the ferroelastic phase transitions in Rb3H(SeO4)2, (NH4)3H(SO4)2 and (NH4)3H(SeO4)2

Optical observations of growth twins and ferroelastic domains and measurements of the rotation of the optical indicatrix were carried out for Rb₃H(SeO₄)₂ and (NH₄)₃H(SO₄)₂ using an optical microscope. Taking into account the symmetry reduction from the rhombohedral (Rm) to the monoclinic phase (B2/a) the occurrence of domains and growth twins can be well described. The orientations of oblique ferroelastic walls are well determined by the spontaneous strains ^s e ₁₁ and ^s e ₂₃ at room temperature.     

Phase transitions in triammonium hydrogen diselenate, (NH4)3 H(SeO4)2

The Raman and infrared spectra of triammonium hydrogen diselenate (NH₄)₃H(SeO₄)₂ (NHSe) have been recorded between 100 and 400 K. The present spectroscopic investigation cofirms the existence of five phases previously observed by other techniques. The analysis shows a progressive ordering with decreasing temperature. The ferroelectric IV → V tansition in this compound is also believed to be of the order-disorder type. The vibrational modes have been assigned by comparison with the sulphate compound (NH₄)₃H(SO₄)₂ (NHS).     

Raman spectroscopic study of the mineral guilleminite Ba(UO2)3(SeO3)2(OH)4·3H2O

The Raman spectrum of the mineral guilleminite Ba[(UO₂)₃O₂(SeO₃)₂](H₂O)₃ was studied and complemented by the infrared spectrum of this mineral. Both spectra were interpreted and compared with the spectra of marthozite, larisaite, haynesite and piretite, all of which should have the same phosphuranylite anion sheet topology. The presence of symmetrically distinct water molecules and hydrogen bonds was inferred from the spectra. This is in agreement with the crystal structural analysis of guilleminite. U O bond lengths in uranyl and O H···O hydrogen bond lengths were calculated from the Raman and/or infrared spectra of guilleminite. Copyright © 2008 John Wiley & Sons, Ltd.     

Proton dynamics in antiferroelectric CsH3(SeO3)2 single crystal investigated by 1H NMR measurements

¹H nuclear magnetic resonance (NMR) measurements have been performed to study the proton dynamics associated with the antiferroelectric transition of a hydrogen-bonded single crystal of CsH₃(SeO₃)₂. Herein, ¹H NMR spectrum, shift, linewidth, and spin-lattice relaxation rate 1/T₁ are measured in the temperature range of 80–296 K with the c-axis parallel to a magnetic field of ~4.85 T. The spectrum exhibits a composite structure with two narrow peaks at 296 K; at a low temperature, this structure evolves into a single broad shape with three humps. This complex shape and evolution are deconvoluted into five or six components based on the number of inequivalent and disordered hydrogen sites. By estimating the chemical shift and linewidth for each proton site, we identify all peaks. The spin-lattice relaxation recovery exhibits a double-exponential behavior with two relaxation times, short T_1S and extremely large T_1L. Both T_1S and T_1L follow Arrhenius behavior. From the respective 1/T₁(T), the activation energies for proton motion are measured to be small: 1.16 ± 0.1 and 0.83 ± 0.06 kJ/mol for T_1S and T_1L, respectively. While the static NMR data, chemical shift and linewidth, show no evidence for the transition, the dynamic data 1/T_1L highlights a clear increase across T_N = 145 K, which is possibly a signature of the transition.     

DSC study of superionic phase transition in (NH4)4H2(SeO4)3 single crystals

DSC and complex impedance studies of the protonic conductor (NH₄)₄H₂(SeO₄)₃, which undergoes a superionic phase transition of first order at T_s = 378 K show that the activation energy of ionic conductivity d(lg σ)/dt and the ordering enthalpy ΔC_p of the crystal are proportional: d(lg σ)/dT = XΔC_p/RT_s + const, as found for MAg₄I₅ crystals undergoing a second-order superionic phase transition. Thus the short-range order environment of the species involved in fast-ion transport plays the main role in the superionic phase transition. This is also supported by the value of the entropy change at T_s, ΔS = 43 J/mole·K. A new metastable phase was found to be induced on heating the (NH₄)₄H₂(SeO₄)₃ crystal above T_s.     

Hypersonic wave anomalies in Cs3H(SeO4)2 at the transitions above room temperature

The elastic properties of Cs3H ( SeO4 ) ₂ are investigated by Brillouin spectroscopy in the temperature range 20-220 covering the two transitions III II and II I occurring at and , respectively. Phase I is known to be a protonic conductive one. Discontinuities of elastic constants are generally observed at both transitions, implying first orderness. In phases II and I, a slight broadening of the Brillouin lines is detected. The results are discussed in comparison with compounds of the families XHSeO4 (X = NH4, Rb and Cs) and CsH2BO4 (B = As and P) which also undergo a transition to a superionic phase. In the conductive phase, it appears that the lattice anharmonicity is weaker in Cs3H ( SeO4 ) ₂ than in these other compounds. Received 16 October 1998     

Raman spectroscopic study of the uranyl selenite mineral demesmaekerite Pb2Cu5(UO2)2(SeO3)6(OH)6·2H2O

The Raman spectrum of the uranyl selenite mineral demesmaekerite was studied, complemented by the infrared spectrum and tentatively interpreted. The observed bands were attributed to the stretching and bending vibrations of (UO₂)²⁺, (SeO₃)²⁻ and OH groupings. U O bond lengths in uranyl and O H···O hydrogen bond lengths were calculated from Raman and/or infrared spectra and compared with published data. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl selenite mineral marthozite Cu[(UO2)3(SeO3)2O2]·8H2O

The mineral marthozite, a uranyl selenite, has been characterised by Raman spectroscopy at 298 K. The bands at 812 and 797 cm⁻¹ were assigned to the symmetric stretching modes of the (UO₂)²⁺ and (SeO₃)²⁻ units, respectively. These values gave the calculated U O bond lengths in uranyl of 1.799 and/or 1.814 Å. Average U O bond length in uranyl is 1.795 Å, inferred from the X‐ray single crystal structure analysis of marthozite by Cooper and Hawthorne. The broad band at 869 cm⁻¹ was assigned to the ν₃ antisymmetric stretching mode of the (UO₂)²⁺ (calculated U O bond length 1.808 Å). The band at 739 cm⁻¹ was attributed to the ν₃ antisymmetric stretching vibration of the (SeO₃)²⁻ units. The ν₄ and the ν₂ vibrational modes of the (SeO₃)²⁻ units were observed at 424 and 473 cm⁻¹. Bands observed at 257, and 199 and 139 cm⁻¹ were assigned to OUO bending vibrations and lattice vibrations, respectively. O H···O hydrogen bond lengths were inferred using Libowiztky's empirical relation. The infrared spectrum of marthozite was studied for complementation. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the schmiederite Pb2Cu2[(OH)4|SeO3|SeO4]

Raman spectroscopy lends itself to the studies of selenites, selenates, tellurites and tellurates as well as related minerals. The mineral schmiederite Pb₂Cu₂[(OH)₄|SeO₃|SeO₄], is interesting, in that, both selenite and selenate anions occur in the structure. Raman bands of schmiederite at 1095 and 934 cm⁻¹ are assigned to the symmetric and antisymmetric mode of the (SeO₄)²⁻ anions. For selenites, the symmetric stretching mode occurs at a higher position than the antisymmetric stretching mode, as is evidenced in the Raman spectrum of schmiederite. The band at 834 cm⁻¹ is assigned to the symmetric (SeO₃)²⁻ units. The two bands at 764 and 739 cm⁻¹ are attributed to the antisymmetric (SeO₃)²⁻ units. An intense, sharp band at 398 cm⁻¹ is assigned to the ν₂ bending mode. The two bands at 1576 and 1604 cm⁻¹ are assigned to the deformation modes of the OH units. The observation of multiple OH bands supports the concept of a much distorted structure. This is based upon the four OH units coordinating the copper in a square planar structure. A single symmetric Raman band is observed at 3428 cm⁻¹ and is assigned to the symmetric stretching mode of the OH units. The observation of multiple infrared OH stretching bands supports the concept of non‐equivalent OH units in the schmiederite structure. Copyright © 2008 John Wiley & Sons, Ltd.     

Mixed alkali metal selenate proton conductors: Phase transitions and crystal structure of [Rb0.54(Nh4)0.46]3H(SeO4)2

Optical birefringence, calorimetric, thermal expansion, powder and single crystal X-ray diffraction investigations of mixed proton conductors [Rb_1-x(NH₄)_x]₃H(SeO₄)₂ were performed with the aim of studying the influence of partial substitution of cations on the superprotonic phase transition, on the atomic structure and on other characteristic features of this type of crystals.     

1H NMR study of N(CH3)4H(ClF2CCOO)2

The proton spin–lattice relaxation times and ¹H NMR second moments were measured over a wide range of temperature. The results were compared with those of the ¹⁹F NMR relaxation that we obtained earlier. For both nuclear species, the evolution of the longitudinal magnetizations with time is observed to be strongly bi-exponential and were in good quantitative agreement with the cross-relaxation theory.     

Ordering of the O(2)…D… O(2) bonds near the phase transition in KD3(SeO3)2 single crystals by D nuclear magnetic resonance

Deuterium resonance investigations of KD₃(SeO₃)₂ single crystals have been performed near the phase transition temperature T _C . There are two types of deuterium bonds in these crystals with different behaviors at this phase transition. Our experimental results show that there are significant changes in the D spinlattice relaxation time T ₁ at T _C ; the abrupt decrease in T ₁ near T _C can be explained by the critical slowing down of an overdamped soft pseudospin-type deuteron mode. Further, the ordering of the O(2)…D… O(2) bonds is affected by the phase transition, whereas the ordering of the O(1)-D… O(3) bonds is unaffected. The D NMR measurements also show that the D(2) deuteron disordering above T _C is dynamic and not static.     

Refinement of hydrogen positions in (NH4)2SeO4

The crystal structure of ammonium selenate has been studied by means of single crystal x-ray and neutron diffraction with the purpose of the refinement of hydrogen positions. The refined hydrogen positions obtained by single crystal neutron diffraction show that N-H bond lengths form a regular tetrahedron in an ammonium ion. The single crystal x-ray diffraction data show that N-H bond lengths are shorter than those obtained by neutron diffraction and are not equal between themselves. Thus, the comparison of the results of x-ray and neutron diffraction allows one to suggest that the shorter N-H bond lengths obtained by x-ray diffraction reflect the distribution of the electron charge density of ammonium ions within the (NH₄)₂SeO₄ crystal lattice. The text was submitted by the authors in English.     

H3 PAuPh与(H3PAu)2(1,4-C6H4)2光谱性质的密度泛函研究

用密度泛函(DFT)方法优化了配合物H3 PAuPh(a),(H3 Pau)2(1,4-C6 H4)2(b)的基态的几何结构,并用含时密度泛函方法计算了它们的吸收光谱.结果表明配合物a与b的最低能量吸收谱线的波长分别为257.5 nm和307.6nm,皆具有C(2p)→Au(6p)电荷转移参与下的Px(芳环)→px>(芳环)跃迁本质,并伴有Au(5d)→Au(6p)的金属中心电荷转移性质.配合物b是由两个配合物a相连接而成,配合物b的分子轨道也是由配合物a的分子轨道组合而成.由于轨道组合中存在px或Px相互作用,配合物b的最低能量吸收谱线的波长大于配合物a的相应值.     

[Fe3O(Ala)6(H2O)3](ClO4)7和[Fe3O(Gly)6(H2O3)(NO3)7)·3H2O]顺磁共振谱及变温磁化率研究

本文通过对[Fe 3O(Ala) 6(H 2O) 3](ClO 4) 7和[Fe 3O(Gly) 6(H 2O) 3](NO 3) 7·3H 2O的ESR谱的解析及变温磁化率的研究,得出它们的ESR谱具有各向同性的特点;朗德因子分别为2.019和1.997;两种配合物中铁离子间有反铁磁相互作用.     

Magnetic studies on synthetic phosphoferrite Fe 3 2+ (H2O)3(PO4)2

Synthetic crystals of phosphoferrite were studied by Mössbauer spectroscopy for temperatures ranging from 4.2 to 17.5 K. The analysis of the behaviour of the hyperfine fields for the two unequivalent sites near the Néel temperature (17.4 K) allowed the determination of the critical exponent for each site as ₁=0.171 and ₂=0.314.