Spin-spin interaction of Ni2+ ions in ZnSiF6·6H2O

The angular dependences of the electron spin resonance spectrum of 1% Ni²⁺ ions in a ZnSiF₆·6H₂O matrix are investigated experimentally at 36 GHz and 4.2 K. Besides the main spectrum of the isolated ion, we observed a spectrum due to interacting pairs of Ni²⁺ ions, located in the first (nn) and second (2n) coordination spheres and coupled by, besides the magnetic dipole-dipole interaction, isotropic exchange: J _nn = (−197±1)×10⁻⁴, J _2nα = (−5±1)×10⁻⁴, and J _2nβ = (3±2)×10⁻⁴ cm⁻¹. Lines due to other isolated Ni²⁺ ions, which have a different initial splitting D, are also present in the spectrum with intensity comparable to the pair spectrum. Low-symmetry distortions of the crystal field are observed, caused by a pair of impurity ions located close to one another. It is shown that the previously proposed interpretation is incorrect. Fiz. Tverd. Tela (St. Petersburg) 41, 1602–1608 (September 1999)     

Study of the structure of FeSiF6·6H2O by EPR and optical spectra

The method for determining the crystalline structure from relevant EPR zero-field splitting and optical spectra data is applied to ferrous fluosilicate (FeSiF₆·6H₂O. The results, consistent with data from Mossbauer and IR magnetic resonance, show that the effective symmetry of the Fe₂₊ site in FeSiF₆·6H₂O is a rhombic distortion rather than a trigonal one (D_3d).     

Crystal structure and Mössbauer spectroscopic study of FeSnF6·6H2O

Large single crystals of FeSnF₆·6H₂O were grown when aqueous hydrofluoric solutions of SnF₂ and FeF₂ were allowed to evaporate in air. Tin-119 Mössbauer spectroscopy at ambient temperature shows a single line at slightly negative isomer shift relative to CaSnO₃ at room temperature (=–0.380(6) mm/s, =0). This is characteristic of tetravalent tin octahedrally coordinated by fluorine. The X-ray crystal structure shows that tin(IV) is coordinated by 6 fluorine atoms, and Fe(II) by 6 water molecules. Both sites show a slight distortion from octahedral symmetry: the six distances are equal (Sn-Fe=1.941(3) Å and Fe-O=2.112(3) Å), whereas there are two values of angles (Fe-Sn-F=90.4(1)° and 89.6(1)°; O-Fe-O=91.1(1)° and 88.9(1)°). The material is an ionic compound [SnF₆]^2–[Fe(H₂O)₆]²⁺.     

Phase transition studies in CoSiF6·6H2O and Co1−xZnxSiF6·6H2O by Mn(II) EPR

Phase transition studies on single crystals of CoSiF₆·6H₂O and Co_1−xZn_xSiF₆·6H₂O (x = 0.082, 0.182, 0.248) using Mn(II) EPR at X-band were carried out in the temperature range 10–300 K. Phase transitions with considerable thermal hysteresis have been detected in CoSiF₆·6H₂O and Co_1−xZn_xSiF₆·OH₂O (x = 0.082, 0.182). In CoSiF₆·6H₂O, the transition temperatures during cooling (T^c_c) and during heating (T^h_c) were found to be considerably less than those obtained previously from magnetic anisotropy experiments, i.e. 230 and 246 K as against 246 and 259 K. These characteristic temperatures for the dilute crystals having x = 0.082 and 0.182 were 205, 218 K and 175, 185 K, respectively. It is thus evident that magnetic dilution with zinc causes a progressive reduction in the transition temperatures as well as in the thermal hysteresis. The phase transition manifests itself in a large discontinuous increase in the Mn(II) zero-field splitting parameter (D), i.e. from −187 ± 1 G to −290 ± 1 G, in these crystals. The hyperfine coefficient (A) also increases discontinuously from 99 ± 1 G to 102 ± 1 G at T_c. In the dilute crystal with x = 0.248 a very slow continuous decrease in D and practically no change in A have been detected with a lowering of the temperature. A small temperature independent positive g-shift (g = 2.020 ± 0.005) has been observed in all the crystals studied. The spin-lattice relaxation time (T₁) of the Co(II) ion in CoSiF₆·6H₂O at different temperatures, both above and below T_c, has been estimated from the observed Mn(II) hyperfine linewidth. A discontinuous change in T₁ at T_c has been observed. Analysis of the temperature dependence of the linewidth has further revealed that a two-level Orbach process describes well the thermal behaviour of the spin-lattice relaxation of the Co(II) ions in these crystals. The location of the first excited level in CoSiF₆·6H₂O determined from such studies at temperatures both above and below T_c has been examined in the light of the ligand field energy scheme of the Co(II) ion in an octahedral field. It is concluded that the phase transition in this crystal is probably accompanied by a change in sign of the axial field parameter (Δ).     

超分子化合物C11H6N2O·H3PO4·H2O的合成与晶体结构

采用水热反应法合成超分子化合物C11H6N2O·H3PO4·H2O,通过元素分析、红外光谱和X射线单晶衍射对其组成、结构进行分析.该化合物属于三斜晶系,空间群P-1,晶胞参数a=0.73350(6)nm,b=0.74191(7)nm,c=1.15692(14)nm,α=96.395(2)°,β=92.9940(10)°,γ=90.3440(10)°,V=0.62477(11)nm3,Z=2,F(000)=308,Dc=1.585g·cm-3,最终偏差因子R1=0.0521,wR2=0.1282.该化合物的不对称单元由3个独立的分子4,5-二氮芴-9-酮、磷酸和水分子构成,氢键连接分子形成三维超分子化合物.     

Incommensurate Phases of the MgSiF6·6H2O Crystals: EPR and Group-Theoretical Studies

The group-theoretical study of the structural phase transition to incommensurate state of MgSiF₆·6H₂O crystals, revealed by the electron paramagnetic resonance (EPR) method, as well as analysis of the EPR results, are presented. The consideration of temperature dependences of Mn²⁺ admixture ion EPR spectrum symmetry and parameters leads to the conclusion that at T _i1 = 370 ± 0.3 K they undergo second-order structural phase transition to incommensurately modulated state, the order parameter of this transition may be the angle of [Mg(H₂O)₆]²⁺ octahedra rotation around crystal C ₃ axis. At temperature decreasing below T _i1 the gradual transformation of plane-wave modulation of lattice displacements into soliton mode occurs, which is interrupted by the first-order phase transition at T _i2 = 343 ± 0.3 K accompanied by abrupt decrease in modulation amplitude. At T _c = 298.5 ± 0.3 K the first-order improper ferroelastic phase transition into monoclinic phase occurs. The group-theoretical analysis of the phase transition at T _i1 in the investigated crystals, carried out for the first time, has shown that the existence of the incommensurately modulated phase is conditioned by the fundamental reasons (presence of Lifshitz invariant). The conclusions of this analysis on the nature of order parameter, the structural motifs of incommensurate phase and the possible character of temperature evolution of the structure are in agreement with the EPR investigation data.     

Spin-lattice relaxation time of Yb3+ in YbCl3·6H2O

Temperature dependence of experimentally determined spin-lattice relaxation time τ_Yb of Yb³⁺ ions in YbCl₃·6H₂O single crystals is examined. It is found that τ_Yb has different temperature dependences in the temperature ranges 2–30 K, 30–77 K, 150–300 K. In particular, Raman mechanisms are found to be predominant in the temperature ranges 2–30 K and 150–300 K, while the direct process is predominant in the range 30–77 K.     

Synthesis of single crystalline (NH4)2V6O16·1.5H2O nest-like structures

Novel nest-like (NH₄)₂V₆O₁₆·1.5H₂O structures made of nanobelts have been synthesized by a facile hydrothermal approach. The powder X-ray diffraction pattern of the sample reveals the monoclinic crystalline phase of (NH₄)₂V₆O₁₆·1.5H₂O. The scanning electron microscopy images of the sample obtained at 130 °C for 3 days exhibit nest-like morphology. The transmission electron microscopy result reveals that the nanobelts have a smooth surface. The selected area electron diffraction pattern of the nanobelts indicates single crystalline nature. The two major weight losses occur in thermogravimetric analysis which correspond to the removal of water and ammonia molecules. Further, calcination of the (NH₄)₂V₆O₁₆·1.5H₂O product results in the formation of orthorhombic phase of shcherbianite V₂O₅.     

Crystal and magnetic properties of the new copper-sodium borate CuNaB3O6 · 0.842H2O

A new compound CuNaB₃O₆ · 0.842H₂O was grown for the first time. Its crystal structure, magnetic susceptibility, and magnetic resonance properties are presented. It was proposed that CuNaB₃O₆ · 0.842H₂O is a spin-Peierls magnet with the transition temperature T _SP ～ 128 K and a ladder spin structure. The possibility of a structural phase transition at T < T _SP is predicted.     

Electronic structure, optical properties and lattice dynamics of MgSO3·6H2O

The electronic band structure, optical properties and lattice vibrations of MgSO(3)·6H(2)O were studied within density functional theory and compared to the experimental optical data and polarized Raman spectra. Due to the 'molecular' nature of the MgSO(3)·6H(2)O crystal all Γ-point phonon modes could be separated into groups belonging to specific structural blocks: Mg(H(2)O)(6) octahedra, SO(3) units and H(2)O molecules. All Raman lines in the experimental spectra are assigned to definite vibrations of the structure and reasonable agreement is found between theoretical and experimental mode frequencies. The temperature-dependent Raman spectra reveal at 60 °C a sharp transition from MgSO(3)·6H(2)O to anhydrous amorphous MgSO(3) without the noticeable presence of intermediate lower hydrates, such as MgSO(3)·3H(2)O.     

Nuclear Magnetic Resonance Relaxation Study of the Phase Transitions of Rb2CuCl4·2H2O and Cs2MnCl4·2H2O Single Crystals

The physical properties and phase transitions of Rb₂CuCl₄·2H₂O and Cs₂MnCl₄·2H₂O crystals were investigated by performing ⁸⁵Rb, ⁸⁷Rb, and ¹³³Cs nuclear magnetic resonance relaxation analyses. The temperature dependences of the spectra and the spin–lattice relaxation times T ₁ near T _C are related to changes in the symmetry of the octahedrons consisting of four Cl⁻ ions and two water molecules around Rb⁺ or Cs⁺; the forms of these octahedrons are disrupted by the loss of H₂O. The difference between the relaxation times of the two crystals is possibly due to the difference between the electron structures of the Cu and Mn ions. Cu²⁺ has nine valence electrons in its 3d orbital, whereas Mn²⁺ has five valence electrons in its 3d orbital.     

Kinetics of Heterogeneous Isotopic Exchange of 60Co/Co3Co(CN)6 2 · 12 H2O in Aqueous Solution

The heterogeneous exchange reaction between cobalt ions in solution and Co₃Co(CN)_{6 2} · 12 H₂O has been studied. It is found that the exchange rate increases as the concentration of Co²⁺ ions in solution decreases. The results show that the exchange rate is controlled by the surface reaction at the solid-liquid interface. The activation parameters E_a, ΔH^#, ΔS^#, and ΔG^# are calculated.     

Thermal Dehydration and Vibrational Studies of ZnK4(P3O9)2 · 6H2O

The thermal dehydration of ZnK₄(P₃O₉)₂ · 6H₂O was studied in the range 25–500°C by thermogravimetric analysis (TGA and DSC) and X‐ray diffraction. We found, based on the TGA and DSC scans, the dehydration of this salt takes place in three stages with a loss of the six water molecules. The infrared and Raman spectra of ZnK₄(P₃O₉)₂ · 6H₂O have been recorded and interpreted using a factor group analysis. The internal modes are assigned in terms of POP and PO₂ structural units using experimental and theoretical IR and Raman frequencies.     

Electron paramagnetic resonance and spinlattice relaxation of Cu2+ ions in ZnSeO4·6H2O

In this paper, we present detailed studies of the EPR spectra of Cu²⁺ ions in single crystals of ZnSeO₄·6H₂O. We describe the spectrum with a rhombic spin Hamiltonian with the following parameters: g_z=2.427; g_y=2.095; g_x=2.097; A _z ⁶⁵ =138.4·10^?4 cm^?1; A _x ⁶⁵ =22.3·10^?4 cm^?1. We studied spin-lattice relaxation in the temperature range 4–300 K at the frequency v≈9.3 GHz. The measured spin-lattice relaxation rate for the orientation H∥L₄ is described well at T<5 K by a linear dependence, while at T>5 K it is described by the sum of three exponentials: $$T_1^{ - 1} = 0.27T + 3.3 \cdot 10^{\text{s}} \exp \left( {\frac{{ - 69.5}}{T}} \right) + 2.6 \cdot 10^7 \exp \left( {\frac{{ - 140}}{T}} \right) + 1.36 \cdot 10^{10} \exp \left( {\frac{{ - 735.6}}{T}} \right){\text{ sec}}^{{\text{ - 1}}} $$ .We discuss possible reasons for the exponential dependence of T ₁ ^?1 for the Raman process.     

Dielectric relaxation of α-cyclodextrin-polyiodide complexes (α-cyclodextrin)2 · BaI2 · I2 · 8H2O and (α-cyclodextrin)2 · KI3 · I2 · 8H2O

The frequency and temperature dependence of the real (ε′) and imaginary (ε″) parts of the dielectric constant of the polycrystalline complexes (α-CD)₂ · Bal₂ · I₂ · 8H₂O and (α-CD)₂ · KI₃ · I₂ · 8H₂O (α-CD = α-cyclodetrin) have been investigated over the frequency and temperature ranges 0–100 kHz and 120–300 K, respectively. The temperature dependences of ε′, ε″ and the phase shift φ show two steps, two peaks and two minima, respectively, revealing the existence of two kinds of water molecule, the tightly bound and the easily movable water molecules, in both complexes. The first peak of (T) or the first minimum of φ(T) presents the transformation of flip-flop hydrogen bonds to the normal state. The second ε″ (T) peak or φ(T) minimum corresponds to the easily movable water molecules or to a partial transformation of tightly bound to easily movable water molecules. For T > 270K both samples show semiconductive behaviour with energy gaps of 1.84eV for the (α-CD)₂ · BaI₂ · I₂ · 8H₂O complex and 1.36eV for the (α-CD)₂ · KI₃ · I₂ · 8H₂O complex. The conductivity at room temperature decreases in the order: (α-CD)₂ · BaI₂ · I₂ · 8H₂O > (α-CD)₂ · LiI₃ · I₂ · 8H₂O > (α-CD)₂ · KI₃ · I₂ · 8H₂O > (α-CD)₂ · Cd_0.5 · I₅ · 26H₂O. The relaxation time varies in a Λ-like curve (from 120 to 250 K) and rises rapidly for temperatures greater than 250 K, indicating the process of ionic movements. The activation energies around the transition temperature 0.98–1.09 k _B T _trans for (α-CD)₂ · BaI₂ · I₂ · 8H₂O and 1.06-1.55 k _B T _trans for (α-CD)₂ · KI₃ · I₂ · 8H₂O reveal the greater stability of the α-K complex against that of the α-Ba complex.     

Effect of the interface heat exchanger in composite NH3/H2OH2O/LiBr absorption-refrigeration systems

In previous publications, a high-efficiency, composite absorption-refrigeration system has been proposed, which was composed of two co-operating absorption units using NH₃/H₂O and H₂O/LiBr solutions, respectively. The heat output from the NH₃/H₂O unit was employed to drive the H₂O/LiBr unit. In the present work, the real performance of the system is predicted and the effect of the heat exchangers connecting the two co-operating units is examined. Under certain assumptions, the real coefficient of performance and other characteristics of the system are expressed in terms of the ambient temperature and the effectiveness, ϵ of the interface heat exchanger. It is found that the effect of the latter is considerable, being more pronounced at the higher values of ϵ. For example, a system operating under usual conditions at 25°C ambient temperature, obtains a theoretical performance coefficient ranging from 108 to 209% for ϵ ranging from 40% to its theoretical value of 100%.     

Effect of synthetic methods on electrochemical performances of VOPO4·2H2O supercapacitor

Ionics - In this paper, we studied the VOPO4·2H2O as an electrode material for supercapacitors. A systematic comparison of VOPO4·2H2O prepared by reflux and hydrothermal methods was...     

Kinetic mechanisms of the uptake of atmospheric gases on the surface of sea salts. ClNO3 uptake on MgCl2 · 6H2O/NaCl

The uptake coefficients γ of chlorine nitrate on MgCl₂ · 6H₂O crystallites and a MgCl₂ · 6H₂O-NaCl mixture deposited from an aqueous solution are measured using a flow reactor with a movable salt-substrate-coated insert equipped in combination with a mass spectrometer at 295–428 K, [ClNO₃] = (0.2?12) × 10¹² cm^?3, and [H₂O] = 1.0 × 10¹² ? 4.3 × 10¹⁵ cm^?3. Immediately after the exposure of the salt substrate to a ClNO₃ flow, γ(t) decreases exponentially with time, γ(t) = γ₀ × exp(?t/τ) + γ _s , to a steady-state level, γ _s , which depends on the temperature and the ClNO₃ and H₂O concentrations. The main gas-phase product is Cl₂, HOCl appears only when water vapor is admitted into the reactor. The coefficient of steady-state uptake on wetted MgCl₂ · 6H₂O at 295 K can be described by the approximation γ = a + b [H₂O] with a = 3.5 × 10^?3 cm³ and b = 3.2 × 10^?18 cm³. The mechanism of the uptake of ClNO₃ on MgCl₂ · 6H₂O is discussed. The experimental data are treated within the framework of a steady-state uptake model to estimate the heat of adsorption of ClNO₃ on MgCl₂ · 6H₂O (Q _ad = 62 kJ/mol) and the activation energy of the bimolecular heterogeneous reaction ClNO₃ + Z _s = 2Cl₂ + Mg(NO₃)₂ · 6H₂O (E _a = 21.8 kJ/mol; Z _s denotes a ClNO₃-MgCl₂ · 6H₂O surface complex). When the MgCl₂ · 6H₂O: NaCl is varied from 0 to ～3 wt %, the steady-state uptake coefficient changes from the value corresponding to uptake on pure NaCl to that characteristic of uptake on pure MgCl₂ · 6H₂O.     

EPR studies of Cu2+ ion in CdK2 (SO4)2·6H2O single crystals

The EPR spectra of Cu²⁺ in CdK₂(SO₄)₂·6H₂O crystals have been studied at 77 K and 300 K in three (bc, a¹c and a¹b) planes. The angular variation spectra showed that the Cu²⁺ ion enters the Cd²⁺ site in the lattice. The principal g and A values, covalency parameter (α'²), mixing coefficients (α and β) and Fermi-contact term (K) have been evaluated from the EPR analysis. The ground-state wave function of the Cu²⁺ ion has been constructed using the α'², α and β values, and the signs for the hyperfine coupling constants are also determined. The covalency value indicates the percentage of unpaired spin density present at the metal (Cu²⁺) d orbital. The nature of the distortion present in the lattice is obtained from the values of the mixing coefficients.