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.     

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.     

Anomalous temperature dependence of Fe3+ quadrupole interaction in (ND4)2FeCl5·H2O

The quadrupole splitting of the title compound was measured in the 12–295 K temperature range. A strong increase of is observed on cooling. This effect can be explained in terms of thermally activated reorientation of the ND ₄ ⁺ ion, which makes a sizeable contribution to the EFG at the Fe site. Analysis of our data yields an activation energy for the ion's hindered rotation,E/k _B=470±30 K. A comparison with previous results for the non-deuterated salt is made.     

The H—H+, H+—H+ and H—H fragmentation in the collision-induced dissociation of H 2 + ions

The collision-induced dissociation of 10 keV H ₂ ⁺ ions incident on H₂ has been studied in this paper. Total cross sections and angle distributions for the H⁺-H, H⁺-H⁺ and H-H fragmentations are given. Distributions over both angle and velocity have been measured for the H-H⁺ and H-H fragmentation.     

Synthesis and optical properties of Co2+ and Ni2+ ions doped β-BaB2O4 nanopowders

Co²⁺ and Ni²⁺ ions doped β-BaB₂O₄ nanopowders have been prepared by co-precipitation method and their structural properties are studied by spectroscopic techniques. Powder XRD data reveals that the crystal structure belongs to monoclinic and the average crystallite size is calculated. Optical absorption spectra data reveal octahedral site symmetry for Co²⁺ and Ni²⁺ ions. Crystal field (Dq) and inter-electron repulsion (B and C) parameters are evaluated for Co²⁺ doped β-BaB₂O₄ nanopowders as Dq=960, B=900 and C=3850 cm^?1 and for Ni²⁺ doped β-BaB₂O₄ nanopowders, Dq=900, B=850 and C=3500 cm^?1. FT-IR spectra showed the characteristic vibrational bands related to BO₃ and BO₄ molecules. Photoluminescence spectra contain the emission bands in ultraviolet and blue regions.     

Inversion of spin levels in Ni2+: Zn(BF4)2 · 6H2O under uniform compression and the effect of transition coincidence

The electron paramagnetic resonance (EPR) spectra of Ni²⁺ ions substituting for Zn²⁺ ions in Zn(BF₄)₂ · 6H₂O crystals are studied over a wide range of temperatures under uniform compression. Measurements are performed in the X-and Q-bands. The parameter D, which characterizes the initial splitting, undergoes considerable variations with changes in temperature and pressure, whereas the g factor remains virtually unchanged. An increase in the temperature is accompanied by a nonlinear increase in D. Under uniform compression, the initial splitting varies linearly and the parameter D changes its sign at 3.5 kbar, which indicates inversion of the spin levels. The coincidence of the EPR lines associated with different transitions leads to the appearance of line-profile dips in the spectra due to cross-relaxation inside the spin system.     

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.     

Some Properties of NiCl2 · 6H2O Single Crystals

Physics of the Solid State - A single crystal of nickel chloride hexahydrate has been grown by isothermal evaporation of a saturated aqueous solution. The transmission-spectrum parameters and...     

Topology of spin Hamiltonian and crystal field tensors for Mn2+ in ZnSeO4·6H2O crystal

The expansion of the {B ₂} and {B ₄} tensors of the spin Hamiltonian (SH) for Mn²⁺ (⁶S-state) is performed in terms of the irreducible tensor products {V _{L 1} ?V _{L 2}}₂ and {V _{L 1} ?V _{L 2}}₄ of the crystal field (CF) tensors {V _{L 1}} and {V _{L 2}}. The EPR spectra of Mn²⁺ in the ZnSeO₄·6H₂O crystal are studied and the SH tensors {B ₂} and {B ₄} are calculated. The tensors {V ₄?V ₄}₂ and {V ₄?V ₄}₄ are computed using the point-charge model (PCM) of the [Zn(H₂O)₆] complex with the C₂ symmetry and are compared with the SH tensors {B ₂} and {B ₄}, respectively. The correct signs of the elements and the pseudo-symmety axes of the tensors are obtained both for the {B ₂} tensor and {V ₄?V ₄}₂ and for the {B ₄} tensor and {V ₄?V ₄}₄. It is concluded that the irreducible tensor products {V ₄?V ₄}₂ and {V ₄?V ₄}₄ provide the predominant contribution respectively to the SH tensors {B ₂} and {B ₄} of Mn²⁺.     

Surface segregation during the uptake of NO3 on coatings composed of NaI · 2H2O/NaBr · 2H2O and MgBr2 · 6H2O/MgCl2 · 6H2O binary salts: Solubility or deliquescence?

The uptake of NO₃ radicals on the surface of coatings prepared from the individual salts of NaI and NaBr dehydrates, hexahydrates of MgBr₂, and MgCl₂ and NaI · 2H₂O/NaBr · 2H₂O and MgBr₂ · 6H₂O/MgCl₂ · 6H₂O binary salts at various mole fractions of the doping salts, NaI · 2H₂O and MgBr₂ · 6H₂O in the initial aqueous solution was measured in a flow reactor by kinetic mass spectrometry. The dependences of the rates of the consumption of the reactant and of the formation of the products on the mole fraction of the doping salt made it possible to determine a quantitative relationship between the surface density of the doping salt and its mole fraction in the initial solution. A joint analysis of these dependences and the previously obtained data led to the conclusion that the deliquescence of the studied individual salts produces the predominant effect on the ratio between their surface densities.     

A possible tricritical line in Ni(NO3)2 · 2H2O

We obtain the behaviour of the critical (possibly tricritical) point for metamagnetic Ni(NO₃)₂·2H₂O as a function of several applied hydrostatic pressures up to 11 kbar. The obtained line of possible tricritical points greatly suggests a pressure induced metamagnetic transition in a 0.8 kbar range.     

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).     

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).     

A quadratic configuration interaction study of N2O and N2O·−

The geometries and vibrational frequencies of both N₂O and N₂O^·– were calculated at the QCISD and QCISD(T) levels of theory using aug-cc-pVDZ and aug-cc-pVTZ basis sets. The electron affinity of N₂O was determined to be ?0.15 eV. This work corroborates an earlier G2 study and suggests that the currently accepted value for the electron affinity, 0.22eV, is in error. This study represents the best calculation to date for the geometry and vibrational frequencies of N₂O^·?     

Luminescence and absorption of Tb3+in mo·Al2O3·B2O3·Tb2O3 glasses

Quantum yields of the green Tb luminescence for 254 nm excitation of glass compositions in the system MO·Al₂O₃· B₂O₃·Tb₂O₃ (M = Mg, Ca, Sr, Ba and Zn) were studied in relation to absorption and excitation spectra. Yields as high as 80% were observed. The Tb 4f-5d absorption maximum ranges from 218 to 232 nm, always at a longer wavelength than the glass matrix absorption. The yield strongly depends on the spectral position of the 4f-5d absorption, due to competing impurity absorption at 254 nm.