27Al Magic Angle Spinning Nuclear Magnetic Resonance Study of Al1−x Cr x K(SO4)2·12H2O (x = 0, 0.07, and 0.2)

The physical properties of Al_1?x Cr _x K(SO₄)₂·12H₂O (x = 0, 0.07, and 0.2) were studied as a function of temperature using magic angle spinning nuclear magnetic resonance for ²⁷Al. On the basis of the physical properties of pure AlK(SO₄)₂·12H₂O, the effects of partially replacing Al³⁺ with Cr³⁺ ions were examined. Molecular motion changed with the concentration of Cr³⁺ ions. The relaxation process near 320 K was found to undergo molecular motion as described by the Bloembergen–Purcell–Pound theory. The activation energies, phase transition temperatures, and spin–lattice relaxation times in the rotating frame T _1ρ changed with the concentration of paramagnetic ions.     

Effect of protonation on individual hydrogen bonds in the 8-oxoguanine-cytosine base pair: NMR,NBO and AIM analyses

Protonation increases the total binding energy of the 8-oxoguanine-cytosine (8OG:C) base pair by 60–70% at the B3LYP/6-311++G(d,?p) level of theory. It changes the individual H-bond energies, estimated from electron charge densities at bond critical points, by 1.16 to ?16.41?kcal?mol^?1. The individual H-bond energies and the two bond X–Y spin–spin coupling constants (^2hJ_X–Y) increase with protonation where 8OG behaves as an H-bond donor; the reverse is true for the H-bonds in which the 8OG unit acts as an H-bond acceptor. Similar to ^2hJ_X–Y, the value of ^1hJ_O–H (a one-bond H?···?Y spin–spin coupling constant) is distance dependent and in linear correlation with the O?···?H distance, but the ^1hJ_N–H values are independent of the N–H distance and the PSO term is the predominant portion in it. The ¹J_X–H spin–spin coupling constant is dominated by the negative FC term for all hydrogen bonds, although the PSO term is the best to investigate the behaviour of ¹J_X–H across the X–H?·?Y H-bond.     

EPR studies of Gd3+-doped Ce2(SO4)3.8H2O and La2(SO4)3.9H2O single crystals

EPR spectra of Gd³⁺-doped Ce₂(SO₄)₃.8H₂O and La₂(SO₄)₃.9H₂O single crystals have been measured with an X-band spectrometer at room and low temperatures. The absolute signs of spin Hamiltonian parameters have been determined for the La₂(SO₄)₃.9H₂O host from intensities of lines at liquid helium temperature; for the Ce₂(SO₄).8H₂O host the lines broaden considerably below 60 K, not permitting the determination of absolute signs of spin Hamiltonian parameters. The data are analysed using a rigourous least-squares procedure, fitting simultaneously all lines obtained for several orientations of the external magnetic field. The zero-field splittings have been computed for both the hosts. The characteristics of EPR spectra of Gd³⁺ in these hosts are compared with those obtained in other rare-earth trisulphate octahydrate hosts.     

EPR and magnetic susceptibility studies of the interaction between Cu2+ and Mn2+ ions in x(CuO·MnO)(1−x)[2B2O3·K2O] glasses

EPR and magnetic susceptibility experiments have been performed on x(CuO·MnO)(1?x)[2B₂O₃·K₂O] glasses with x varying in the range 0?x?50 mol.%. For x?3 mol.% both Cu²⁺ and Mn²⁺ ions are present mostly as the isolated species. The increase of the g-tensor values and bonding parameters (α², β², δ²) for Cu²⁺ ions together with the increase of TM ions concentration in the 0.2–1 mol.% range was noticed. In the case of 5 ? x ? 30 mol.% the dipole-dipole and superexchange interactions occur between transition metal ions, the first type of interactions prevailing in this range of concentration. For x30 mol.% the superexchange interaction prevail. The strong interaction between Cu²⁺ and Mn²⁺ gives rise to the exchange coupled Cu²⁺Mn²⁺ pairs in the studied glasses with x 3 mol.%.     

Relaxationsphänomene in Mössbauerspektren von Magnetisierten paramagnetischen Substanzen. I [(Fe x,Al1-x )NH4(SO4)2· 12H2O]

The Fe³⁺-spin in alums of type (Fe _x , A1_1-x )NH₄(SO₄)₂ · 12 H₂O interacts (i) with the crystal lattice viaLS-coupling, and (ii) with the spins of the adjacent Fe³⁺-ions via magnetic dipole-dipole interaction. These interactions lead to a time fluctuation of the spin direction, characterized by correlation times τ _c and τ′ _c of increasing order. The times may be deduced from the⁵⁷Fe-Mössbauer spectra of the alums, τ _c from the width, and τ′ _c ≈τ _c from the position of the hyperfine structure lines. The theoretical interpretation of the Mössbauer spectra is relatively simple, when (i) the spin-lattice interaction gets frozen in, and (ii) a strong applied magnetic fieldH _a decouples the spins of the Fe³⁺-ion and the⁵⁷Fe-nucleus. The spectra were taken, therefore, at 4.2 °K and 8 kOe≦H _a ≦ 54 kOe. According to the 1/r ³-dependence of the magnetic dipole-dipole interaction τ _c should be related tox, the Fe-concentration, τ _c ·x≈τ₀=const. Forx≧0.5 our experimental results are in agreement with this rule when τ₀=(1.5±0.5) · 10^?9 s. For an alum withx=0.26, however, the observed spectra cannot be explained in terms of temporal spin fluctuations, at least not in the framework of the models which are available now. Here, presumedly, the electron spins of adjacent Fe³⁺-ions are coupled to more or less isolated and, consequently, relatively stationary spin clusters of various sizes, leading to many time independent internal magnetic fields. A treatment of this proposal is in preparation.     

Microscopic evidence for a new type of ordering of spin components in a random mixture with competing magnetic anisotropies

The Mössbauer spectroscopy was applied on a random mixture of two kinds of magnetic ions with competing anisotropies, Fe_1?xCo_xCl₂·2H₂O. The Mössbauer spectra observed in the Co(Fe)-rich antiferromagnetic (AF) phase near the tetracritical point show that, although the m₂(m₁) spin component parallel to the easy axis of pure FeCl₂·2H₂O(CoCl₂·2H₂O) has no long-range order in this phase (from the neutron diffraction experiment), the m₂(m₁) spin component contributes to the magnetic hyperfine field at ⁵⁷Fe nuclei as well as the m₁(m₂) spin component (which has a long-range order). This fact indicates that the m₂(m₁) spin components exists in the Co(Fe)-rich AF phase near the tetra-critical point at least in a time scale of ～ 10^?8s. This result predicts that the antiferromagnetic ordering in the Co(Fe)-rich AF phase is a new type one. The new phase observed in the intermediate concentration region is demonstrated as the “mixed ordering” phase.     

Mixed valence states in cobalt iron cyanide

Cobalt iron cyanide with both Co and Fe in mixed valence states were prepared and characterized. In this mixed valence system the cobalt atom is found both as high spin Co(2+) and low spin Co(III) while iron always appears in low spin state to form two solid solutions: Co(2+)Co(III) hexacyanoferrates (II,III), and Co(2+)Co(III) hexacyanoferrate (II). Such solid solutions have the following formula units: (Co²⁺)_x(Co^III)_1−xK[(Fe^II)_1−x(Fe^III)_x(CN)₆]·H₂O and (Co²⁺)_1.5x(Co^III)_1−xK[Fe^II(CN)₆]·yH₂O (0?x?1, 1?y?14). Compounds within these two series were characterized from Infrared, Mössbauer, X-ray diffraction and thermo-gravimetric data, and magnetic measurements at low temperature. A model for their crystal structure is proposed and the structure for a representative composition refined from XRD powder patterns using the Rietveld method. A simple and reproducible procedure to prepare these solid solutions is provided. Within hexacyanoferrates, such mixed valence states system in both metal centres shows unique features, which are discussed from the obtained data.     

Long-lived diatomic dications: potential curves and radiative lifetimes for CaBr2+ and CaI2+ including relativistic effects

Relativistic effective core potential calculations have been employed in the framework of a spin–orbit configuration interaction to compute the lowest-lying electronic states of the CaBr²⁺ and CaI²⁺ dications, and the results are compared with the data for the isovalent CaCl²⁺ system studied earlier. The ground X²Π state in all three dications arises from a strong polarization of X(²P°)(X= Cl, Br or I) by the Ca²⁺(¹S) ion and is bound by 0·96–1·55eV with respect to the corresponding diabatic dissociation limits. It is split by the spinorbit interaction into the X₁ ²Π_3/2 and X₂ ²Π_1/2 components, with the energy splittings calculated to be 647 cm^-1(CaCl²⁺), 2115 cm^-1(CaBr²⁺) and 3544 cm^-1(CaI²⁺). The X₁ and X₂ states are found to be thermodynamically stable in CaCl²⁺ and CaBr²⁺, while in CaI²⁺ the lowest dissociation limit, Ca⁺+(²S)+ I^{+ 3}P₂), lies 1700 and 5200 cm^-1 lower than the X₁ and X₂ minima respectively. The X₁ and X₂ states in CaI²⁺ are extremely long-lived, however, owing to the high and very broad potential barriers to dissociation. The first electronic excited state, A²σ⁺, is also bound in all the above systems, although it is pre-dissociated in CaBr²⁺and CaI²⁺ at large internuclear distances. All other low-lying electronic states of CaX²⁺ are repulsive. Electric-dipole moments are calculated for the A→ X₁, X₂ transitions. The corresponding radiative lifetimes are found to be very long in CaCl²⁺ : τ(A→X₁) = 19·3 ms and τ(A→X₂) = 9·9 ms (the values are given for ν' = 0), and become very significantly shorter for CaBr²⁺ and CaI²⁺ because of the stronger spin-orbit interaction in the heavier systems. This effect is especially noticeable for the A →X₂ transitions, for which the values are computed to be 364 μs in CaBr²⁺ and 50·3 μs in CaI²⁺. The theoretical data obtained should aid in the future spectroscopic detection of these species. To data no experiment of this type has been successfully carried out for any of the thermodynamically stable diatomic dications.     

Paramagnetische Relaxation im Holmiumäthylsulfat

The paramagnetic relaxation of Ho _x Y_1?x (C₂H₅SO₄)₃·9H₂O (x=1; 0.14; 0.1) was investigated with a mutual inductance bridge with frequencies fromν=10 sec^?1 toν=10600 sec^?1 in the temperature range betweenT=1.14°K and 2.11°K. In the diluted samples there is a strong influence of cross relaxation processes between the hyperfine levels on both the paramagnetic relaxation and the paramagnetic susceptibility. One and two spin cross relaxation processes were found. The susceptibility measured as a function of frequency is compared with the susceptibility calculated from the known energy levels of Ho(C₂H₅SO₄)₃·9H₂O. Thus the way how the relaxation process takes place between the various systems (crystal field-, Zeeman-, dipol dipol coupling-, hyperfine structure-, lattice- and bath-system) can be deduced. Some preliminary measurements atν=24.10⁶ sec^?1 are reported and discussed.     

Fluoreszenzlebensdauern einiger wasserhaltiger Salze des Europiums und des Terbiums

At 300°K the fluorescent lifetimes of the levels⁵D₀ of Eu³⁺ and⁵D₄ of Tb³⁺ were measured in the RE(C₂H₅SO₄)₃·9H₂O, RE(BrO₃)₃·9H₂O, RECl₃·6H₂O, RE(NO₃)₃·6H₂O and (RE)₂(SO₄)₃·8H₂O. The fluorescent lifetimes of the above mentioned hydrated crystals are preliminary determined by radiationless transitions. An empirical relation can be obtained for the probabilityw for the radiationless transitions of the formw=const·α _RE·α _Lattice. The factorsα _RE andα _Lattice depend only on the rare-earth ion or the lattice respectively. A structure of the interaction Hamiltonian between the rare-earth ion and the lattice is proposed, which leads to the empirically found relation. The influence of electron- andX-irradiation on the lifetime of the level⁵D₄ in TbCl₃·6H₂O was investigated at 77°K. A decrease of the lifetime and a nonexponential decay of the fluorescence were found. By heating up the crystal to room temperature thermoluminescence and annealing of the irradiation defects are observed.     

EPR Investigation of Exchange Interactions Between Neodymium Ions in {[Nd2(α-C4H3OCOO)6(H2O)2]} n

Electron paramagnetic resonance (EPR) of a new compound {[Nd₂(α-C₄H₃OCOO)₆(H₂O)₂]} _n composed of Nd³⁺–Nd³⁺ dimers is reported. The anisotropy parameters of the spin–spin interaction are determined by fitting experimental and simulated spectra in X- and Q-bands. It is shown that the anisotropy of the exchange interaction gives the main contribution to the anisotropy of the spin–spin interaction. The observed anisotropy disagrees with the expected in the model of the isotropic exchange interaction between real spins. A feature of the EPR spectrum not described by the model of the isolated Nd–Nd dimers and reflecting the magnetization transfer between dimers is detected. The magnetization transfer due to both the relaxation transitions and the interdimer interaction is considered.     

The Application of Raman Spectroscopy to the Study of the Uranyl Mineral Coconinoite Fe2Al2(UO2)2(PO4)4(SO4)(OH)2 · 20H2O

ABSTRACT

Raman spectra of the uranyl-containing mineral coconinoite, Fe₂Al₂(UO₂)₂(PO₄)₄(SO₄)(OH)₂ · 20H₂O, are presented and compared with the mineral's infrared spectra. Bands connected with (UO₂)²⁺, (PO₄)^3?, (SO₄)^2?, (OH)^?, and H₂O stretching and bending vibrations are assigned. Approximate U?O bond lengths in uranyl, (UO₂)²⁺, and O?H…O hydrogen bond lengths are calculated from the wavenumbers of the U?O stretching vibrations and (OH)^? and H₂O stretching vibrations, respectively, and compared with published data for similar natural and synthetic compounds.     

NMR Investigations of the Protonic Transport Mechanism in Composed Materials on the Basis of Cesium Acid Sulfates and Phosphates

The composite materials Cs(HSO₄)_1?x (H₂PO₄) _x were investigated by X-ray phase analysis, differential scanning calorimetry, nuclear magnetic resonance (NMR) relaxation, pulsed field gradient NMR (PFG-NMR) and impedance spectroscopy. Three composite materials types x = 0.1 ÷ 0.3 mixture CsHSO₄, α-Cs₃(HSO₄)₂(H₂PO₄), β-Cs₃(HSO₄)_2.5(H₂PO₄)_0.5—compositions of area I; x = 0.4 ÷ 0.5 mixture α-Cs₃(HSO₄)₂(H₂PO₄) and Cs₂(HSO₄)(H₂PO₄)—compositions of area II; x = 0.6 ÷ 0.9 mixture Cs₂(HSO₄)(H₂PO₄) and CsH₂PO₄—compositions of area III, were synthesized. The phase transition temperature from the low-to-high conductive phase for obtained composite materials is notably below (about 100 °C) than that for the individual components. The proton self-diffusion coefficients measured by PFG-NMR are lower than the diffusion coefficients calculated from proton conductivities data. The correlation times τ _d controlling the ³¹P–¹H magnetic dipole–dipole interaction were calculated according to data of the spin–lattice relaxation on ³¹P nuclei. The self-diffusion coefficients estimated from the Einstein equation are in good agreement with the experimental self-diffusion coefficients measured by PFG-NMR. It confirms the fact that the proton mobility is caused by the rotation of PO₄ anion tetrahedra.     

Analysis of Dissociation—Recombination Processes for the CO<Subscript>2</Subscript> Molecule with the Spin—Orbit Coupling Taken into Account

The dissociation CO₂(X¹Σ) + M → CO(X¹Σ) + O(³P) + M and recombination CO(X¹Σ) + O(³P) + M → CO₂(X¹Σ) + M processes are considered with the spin—orbit coupling taken into account in the ground and several excited states of the CO₂ molecule. Because of the specific features of mutual position of potential energy surfaces of the CO₂ molecule in the ground and several excited states and the large values of spin—orbit interaction matrix elements, which causes the quantum nonadiabatic transition of the molecule from one state to another, these processes become effectively spin-allowed and the rate constants for the nonadiabatic reactions have large values. The proposed dissociation and recombination mechanisms include reactions involving singlet—triplet crossings.     

Hall effect in CeAl3

We have studied temperature dependences of the Hall coefficient R_H(T) and resistivity ?(T) in substitutional solid solutions Ce_xLa_1?xAl₃ (0 ≤ x ≤ 1) which realize the transition from Kondo impurity regime (X?1) to Kondo lattice (X = 1). Lowering temperature results in the anomalous increase of R_H(T). The ratio r = R_H(3 K)/R_H(100 K) has been found to increase with cerium content up to the r ? 15 in the marginal compound CeAl₃. The specific features of R_H(T) behaviour in Ce_xLa_1?xAl₃ alloys seem to be related to the existence at low temperatures of heavy fermions due to the formation of the narrow Abrikosov-Suhl resonance at the Fermi level.     

Synthesis of anionic clay minerals (mixed metal hydroxides,hydrotalcite)

A number of approaches to the synthesis of a class of anionic clay minerals (M_a²⁺M_b³⁺ (OH)_2a+2b(X⁻)_2b ·xH₂O; M²⁺ = Mg, Ni, Co, Zn, Cu, etc.; M³⁺ = Al, Cr, Fe, Sc; M²⁺/M³⁺ ∼ 1−5; X⁻ = water and base stable anion; x = 0−6) have been sumarized. The most general method involves the mixing of a concentrated, aqueous solution of M²⁺ and and M³⁺ with aqueous hydroxide-carbonate to yield an amorphous gel followed by crystallization at 60–325°. For a number of these materials, the synthetic latitudes with respect to the nature of M²⁺, M³⁺, the M²⁺/M³⁺ ratio, the solution pH and the crystallization temperature has been detailed. The crystallization temperature and time influences the particle size, morphology, surface area and the appearance of foreign phases. The incorporation of various interstitial anions by exchange or synthesis is discussed.     

Control of Charge Transfer Phase Transition in Iron Mixed-Valence System (n-C n H2n+1)4N[FeIIFeIII(dto)3] (n=3–6; dto = C2O2S2)

The spin flop behaviour of low anisotropy Mn ions within the mixed halide (⁵⁴Mn)Mn(Br _x Cl_1−x )₂·4H₂O is shown to be interpolative with that of the two terminal compounds, in striking contrast with the dynamics of nuclear spin lattice relaxation.     

The valence states of manganese ion in potassium-borate oxide glasses

EPR and magnetic susceptibility measurements have been performed on xMnO·(1-x) [2B₂O₃·K₂O] with 0?x?50 mol %. The X-ray diffraction analysis showed that in this glass system homogeneous glasses are formed up to x = 70 mol %.EPR and magnetic susceptibility data have shown that in the glasses with x ? 5 mol % only Mn²⁺ ions are present as magnetically isolated species. EPR spectra are modified with the increasing of manganese ions content. In the concentration range 0.5 ? x ? 5 mol %, the spectra are characterized by appearance of three resonance absorptions at g ? 4.3 and g ? 3.3 without hyperfine structure, and at g ? 2.0 with hyperfine structure. For the glasses with x >62; 5 mol %, the resonance spectra are characterized by the appearance of the broad line at g ? 2, characteristic for clustered ions. The magnetic susceptibility data suggest the appearance of superexchange interactions for x >62; 5 mol %. From Curie constant values and qualitative chemical analysis we have established that in the glasses with x ? 10 mol % both, Mn²⁺ and Mn³⁺ ions are present.     

Spin dynamics in the impurity-doped one-dimensional heisenberg paramagnet (CH3)4NMn(1-x)CuXCl3: Nuclear magnetic relaxation

Proton spin-lattice relaxation rate has been measured at room temperature in the impurity-doped (CH₃)₄NMn_(1-x)Cu_xCl₃ for X = 0.04, 0.1 and 0.17. The result for Hz. snfc;chain-axis as a function of resonance frequency clearly shows that the spectral density of the spin fluctuations in the impure system remains to have the characteristics 1-D diffusive term (ω^{-$\text{1}\text{2}$}), with a slower rate of the spin diffusion in accordance with the theory by Richards. The result for H⊥ chain-axis indicates, however, the existence of a singularity of the fluctuations near ω = 0.