The cation ordering in iron-containing zinc and magnesium orthophosphates determined from Mössbauer spectroscopy

The cation distribution between five- and six-coordinated sites in the isotypic solid solutions γ (Zn, Fe)₃(PO₄)₂ and (Mg, Fe)₃(PO₄)₂ has been determined by means of Mössbauer spectroscopy. Iron is found to be strongly ordered into the six-coordinated sites of γ-(Zn, Fe)₃(PO₄)₂ thus stabilizing this phase with respect to α-Zn₃(PO₄)₂, while (Mg, Fe)₃(PO₄)₂; shows a roughly random cation distribution. Distortion of the coordination polyhedra around iron is suggested to limit the solid solution range of iron in the γ-Zn₃(PO₄)₂ structure type. Isomer shifts for Fe²⁺ in the five-coordinated site are observed to be $\text{1.12±0.01}\text{mm}\text{s}$ at room temperature and $\text{1.24±0.02}\text{mm}\text{s}$ at 77 K.     

Structure,vibrational study and conductivity of the trihydrated uranyl bis(dihydrogenophosphate): UO2(H2PO4)2·3H2O

The X-ray structure (293 K) of UO₂(H₂PO₄)₂·3H₂O has been refined (R = 0.062): M_r = 518g, space group: P2₁/c (Z = 4); $\text{a = 10.816(1)}\text{A}\text{?}$, $\text{b = 13.896(2)}\text{A}\text{?}$, $\text{c = 7.481(1)}\text{A}\text{?}$, β = 105.65(1)^°, $\text{V = 1082.7(2)}\text{A}\text{?}{}^3$; D_c = 3.17 Mg m^?3. The structure consists of infinite chains along the (101) axis with U atoms bridged by two H₂PO₄ groups. The U atom is surrounded by a pentagonal bipyramid of oxygen atoms, one of them being an equatorial water molecule. The cohesion between the chains is ensured by hydrogen bonds involving the two last water molecules. An assignment of IR and Raman bands with isotopic substitution spectra is proposed. A phase transition at 128 K was made evident by DSC and spectroscopy. The room-temperature phase is characterized by a high disorder of the OH bond orientation while in the low-temperature phase H₂O and POH species appear well oriented. The conductivity seems to occur by proton transfer and protonic-species rotation at the POH-water molecular interface between the chains. ac conductivity has been determined by means of the complex-impedance method ($\text{σ}{}_{\mathrm{<mtext>RT</mtext>}}\text{～ (3?12) × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$; E ～ 0.20 eV).     

The crystal structures of the ion conductors (NH+4)Zr2(PO4)3and (H3O+)Zr2(PO4)3

The crystal structures of (NH⁺₄)Zr₂(PO₄)₃ and (H₃O⁺)Zr₂(PO₄)₃ have been determined from neutron time-of-flight powder diffraction data obtained at 15 K. Both compounds are rhombohedral, $\text{R}\text{3}\text{c}$, with cell parameters a=8.7088(1) and c=24.2197(4) Å for the ammonium compound and a=8.7528(2), c=23.6833(11) Å for the hydronium compound. In both cases the ions are completely localized in the type I cavities and hydrogen bonded to lattice oxygens. The measured unit cell parameters are relatively large for this class of compounds but the entrance ways into the cavities are still too small to allow for unrestricted movement of the ions. Thus the low conductivity of the hydronium ion is related to this and other structural features.     

Electronic-excitation transfer collisions in flames—V. Cross sections for quenching and doublet-mixing of K(42P)-doublet by N2, O2, H2 and H2O

Weighted average cross sections for quenching of the K(4²P)-doublet by N₂, H₂, O₂ and H₂O, measured in flames, show no significant temperature dependence in the range from 1500 to 2500K. Doublet mixing cross sections for K(4²P$\text{3}\text{2}$?4²P$\text{1}\text{2}$) transitions were measured at 1720K for N₂, O₂, H₂O. The ratios of both mixing cross sections were measured independently and were found to agree with the detailed balance condition within 2 per cent. It is shown that an ionic intermediate-state model cannot explain the large magnitude of N_2? mixing cross sections.     

Interference effects in 12C(p, γ)13N and direct capture to unbound states

Excitation functions of the capture reaction ¹²C(p, γ₀)¹³N have been obtained at θ_γ = 0° and 90° and E_p = 150–2500 keV. The results can be explained if a direct radiative capture process, E1(s and d → p), to the ground state in ¹³N is included in the analysis in addition to the two well-known resonances in this beam energy range $\text{[E}{}_{\mathrm{p}}\text{= 457(}\text{1}\text{2}{}^{\mathrm{+}}\text{)}$ and 1699 $\text{(}\text{3}\text{2}{}^{\mathrm{?}}\text{) keV]}$. The direct capture component is enhanced through interference effects with the two resonance amplitudes. From the observed direct capture cross section, a spectroscopic factor of C²S(l = 1) = 0.49 ± 0.15 has been deduced for the $\text{1}\text{2}{}^{\mathrm{?}}$ ground state in ¹³N. Excitation functions for the reaction ${}^{12}\text{C(p,γ}{}_1\text{p}{}^1\text{)}{}^{12}\text{C}$ have been obtained at θ_γ = 0° and 90° and E_p = 610–2700 keV. Away from the 1699 keV resonance the capture γ-ray yield is dominated by the direct capture process E1 (p → s) to the $\text{2366 (}\text{1}\text{2}{}^{\mathrm{+}}\text{) keV}$ unbound state. Above E_p = 1 MeV, the observed excitation functions are well reproduced by the direct capture theory to unbound states (bremsstrahlung theory). Below E_p = 1 MeV, i.e., E_p → 457 keV, the theory diverges in contrast to observation. This discrepancy is well known in bremsstrahlung theory as the “infrared problem”. From the observed direct capture cross sections at $\text{E}{}_{\mathrm{p}}\text{? 1 MeV}$, a spectroscopic factor of C²S(l = 0) = 1.02 ± 0.15 has been found for the $\text{2366 (}\text{1}\text{2}{}^{\mathrm{+}}\text{) keV}$ unbound state. A search for direct capture transitions to the $\text{3512 (}\text{3}\text{2}{}^{\mathrm{?}}\text{)}$and $\text{3547 (}\text{5}\text{2}{}^{\mathrm{+}}\text{) keV}$ unbound states resulted in upper limits of C²S(l = 1) ≦ 0.5 and C²S(l = 2) ? 1.0, respectively. The results are compared with available stripping data as well as shell-model calculations. The astrophysical aspect of the ¹²C(p, γ₀)¹³N reaction also is discussed.     

Electrical conduction and 1ƒ noise in Li-DOPED MnO

Electrical resistivity, thermoelectric power and current noise were measured on Li-doped MnO single crystals in the temperature range from 300 to 1000 K. Below 700 K the crystals are p-type and the activation energy of the resistivity is 0.75 eV. Around 700 K the activation energy changes from 0.75 to 1.25 eV owing to a change from p- to n-type conduction. The depth of the Li acceptor is found to be 0.65 eV. From resistivity and thermoelectric power data it is concluded that the bandgap in first approximation can be written as E_s(T) = E_o ? γT between 750 and 1000 K, with E_o = 1.9 eV and γ = 6 × 10^?4 eV/K. The current noise spectra show $\text{1}\text{?}$ noise. The magnitude of the $\text{1}\text{?}$ noise is strongly temperature dependent. From the noise data it is deduced that E_o = 2.2 eV and γ = 10^?3 eV/K in the temperature range 430–700 K.     

On the transverse electrical susceptibilities of KDP type crystals

Using statistical Green's function technique exact expression for the transverse electrical susceptibility (x_$\text{a}$) for KDP type crsytals has been derived with the total pseudo-spin lattice coupled mode Hamiltonian. Very good fittings of the experimental data of x_$\text{a}$ for KH₂PO₄, RbH₂PO₄ and KH₂AsO₄ with the derived expression have been obtained with a single set of Blinc-de Geenes (BG) parameters being different for different salts. The temperature dependence of the E-mode character along the transverse $\text{a}$-axis has also been studied theoretically and compared with the recent experimental results available for KH₂PO₄ only.     

Hole contribution to the elastic constants of SnTe

Ultrasonic wave velocities have been measured in SnTe single crystals with hole concentrations of 1.0 and 4.5 × 10²⁰/cm³. The shear elastic stiffness constant C₄₄ is sensitive to the hole concentration but $\text{1}\text{2}\text{(C}{}_{11}\text{? C}{}_{12}\text{)}$ is not, a result which is consistent with the valence band pockets being sited at the L points. The non-ellipsoidal, non-parabolic multivalley band model has been used to calculate the hole contribution to the elastic constants. The calculated difference between the shear constant C₄₄ (2.78 × 10¹⁰ dyne cm^-2) for the two crystals is in agreement with that measured experimentally (2.67 × 10¹⁰ dyne cm^-2). The shear deformation potential constant E_u for the SnTe valence band is 7.8 eV at 293°K.     

The polarization of protons from the 2H(d, p)3H reaction for deuteron energies below 1 MeV

The angular distribution of proton polarization P^γ' (θ) from the ${}^2\text{H}\text{(}\text{d,}\text{p}\text{)}{}^3\text{H}$ reaction has been measured at 975 keV deuteron energy. Moreover, the energy dependence of P^γ′(E_d) was measured at 45°(lab) for deuteron energies between 250 and 975 keV. The values of σ₀(θ)P^γ' (θ) were fitted in terms of an associated Legendre polynomial expansion. The measured energy dependence of P^γ' (E_d) has been analyzed in terms of barrier-penetration parameters.     

Absorption spectra of Ni2+ in (NH4)2Mg(SO4)2·6H2O and Co2+ in Na2Zn(SO4)2·4H2O

Optical absorption spectra of Ni²⁺ in (NH₄)₂Mg(SO₄)₂·6H₂O and Co²⁺ in Na₂Zn(SO₄)₂·4H₂O single crystals have been studied at room and liquid nitrogen temperatures. From the nature and position of the observed bands, a successful interpretation could be made assuming octahedral symmetry for both the ions in the crystals. The splitting observed for ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band in Ni²⁺ and ${}^4\text{T}{}_{\mathrm{2g}}\text{(F)}$ band in Co²⁺ at liquid nitrogen temperature have been explained as due to spin-orbit interaction. The extra band observed at 16,325 cm^-1 in the case of Ni²⁺ at low temperature has been interpreted to be the superposition of vibrational mode of SO^2-₄ radical on ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band. The observed band positions in both the crystals have been fitted with four parameters B, C, Dq and ζ.     

The (p,t) reaction on 12C, 54Fe and 208Pb at 80 MeV

Angular distributions have been measured for the low-lying levels of the residual nuclei for the ¹²C, ⁵⁴Fe and ²⁰⁸Pb(p, t) reactions at E_p = 80 MeV. The shapes of these angular distributions are generally well reproduced by the zero-range distorted-wave Born approximation (DWBA). Enhancement factors extracted from the data show that the DWBA predicts relative strengths consistent with those observed at lower bombarding energies. However, the overall empirical DWBA normalization at E_p = 80 MeV is observed to be $\text{1}\text{12}$ ($\text{1}\text{4}$) of that required at 40 MeV for ²⁰⁸Pb (⁵⁴Fe).     

Particle-hole states in 42K studied by the 44Ca(d, α)42K reaction

The ⁴⁴Ca(d, α)⁴²K reaction was studied at a bombarding energy of 11 MeV using a broadrange magnetic spectrograph and solid-state detectors. About thirty energy levels were identified in ⁴²K, up to an excitation energy of 3.5 MeV. Excitation functions corresponding to some of the low-lying energy states of ⁴²K were measured in the incident energy range from 10.4 to 11.6 MeV. Angular distributions of the α-particle groups corresponding to the excitation of about twenty energy levels in ⁴²K have been measured. DWBA calculations were performed and L-values for most of the above transitions were deduced. The results were compared with previous information and possible spin and configuration assignments are proposed for some of the states. Centroids of states interpreted as belonging to the (1d_{$\text{3}\text{2}$}^?1)_p (1f_{$\text{7}\text{2}$}³)_n, (2s_{$\text{1}\text{2}$}^?1)_p (1f_{$\text{7}\text{2}$}³)_n and the (1d_{$\text{3}\text{2}$}^?1)_P (1d_{$\text{3}\text{2}$}^?1 1f_{$\text{7}\text{2}$}⁴)_n configurations were found to be in good agreement with calculations based on the weak-coupling model.     

The elastic behaviour of the ternary zincblende structure semiconductor CuGe2P3

A single crystal has been grown of CuGe₂P₃, a ternary semiconductor with a zincblende structure in which the copper and germanium atoms are randomly distributed on the cation sites. The second order elastic constants measured by the ultrasonic pulse echo overlap technique (C₁₁ = 13.66, C₁₂ = 6.17, C₄₄ = 6.66 and bulk modulus B = 8.67 in units of 10¹⁰Nm^?2 at 291 K) are closely similar to those of GaP and conform well to Keyes' correlation for zincblende structure crystals. The hydrostatic pressure derivatives of the second order elastic constants ($\text{?C}{}_{11}\text{?P}\text{= 4.40}$, $\text{?C}{}_{12}\text{?P}\text{= 3.9}$, $\text{?C}{}_{44}\text{?P}\text{= 0.93}$ and $\text{?B}\text{?P}\text{= 4.07}$) and the third order elastic constants (C₁₁₁ = ? 8.45, C₁₁₂ = ? 3.49, C₁₂₃ = ? 1.13, C₁₄₄ = ? 2.82, C₁₅₅ = ? 1.44 and C₄₅₆ = ? 0.69 in units of 10¹¹Nm^?2) also resemble those of GaP: even the anharmonicity of the long wavelength acoustic modes of this ternary semiconductor resembles that of its binary “parent” compound. The positive signs of the hydrostatic pressure derivatives and the negative signs of the third order elastic constants show that the acoustic modes at the long wavelength limit stiffen under pressure, an effect which is quantified here by computation of the mode Grüneisen parameters, which are all positive. The harmonic and anharmonic force constants, obtained in the valence force field model, fit well into the pattern shown by related zincblende structure compounds: the ratio ($\text{β}\text{α}$) for bond bending (β) to stretching (α) force constants is greater than 4:1; the dominating anharmonic force constant is γ: most of the anharmonicity is associated with nearest neighbour atoms. Analysis of the temperature dependence of the elastic constants on the basis of a simple anharmonic model again emphasises the similarity between the elastic behaviour of CuGe₂P₃ and GaP. The thermal expansion of CuGe₂P₃ varies almost linearly with temperature between 291 K and 1000 K, the linear coefficient of thermal expansion α being 8.21 ± 0.02 × 10^?6 °C^?1. The similar lattice parameters and elastic behaviour of CuGe₂P₃ and GaP indicate that semiconducting devices made of epitaxial deposits of CuGe₂P₃ on a GaP substrate should prove to be almost strain-free.     

Neutron scattering study of the phase transition in s-triazine at high pressure

The elastic transition in s-triazine (C₃N₃H₃) from a trigonal ($\text{R}\text{3}\text{c}$) high temperature (low pressure) structure to a monoclinic (C2/c) low temperature (high pressure) phase has been investigated at pressures up to 5 kbar using neutron scattering techniques. Neutron diffraction was used to measure the pressure dependence of the order parameter and inelastic scattering to study the softening of the transverse acoustic phonon modes on three isotherms. In both cases the effect of pressure on the transition is found to be described primarily by that on the temperature of the transition.     

Evidence for assignment of 14.0 MeV state in 11B from 10B(n,n)10B

The differential cross section and polarization for neutrons scattered from ¹⁰B have been measured at E_n = 2.63 MeV (E_x = 13.85 MeV). The results of this experiment and other available neutron scattering data in the range 1 < E_n < 4 MeV are interpreted through a single-level R-matrix calculation over the region 12 < E_x < 15 MeV. Based on this analysis the most probable J^π assignment for the 14.0 MeV level in ¹¹B is $\text{11}\text{2}{}^{\mathrm{+}}$. The anomaly near E_x = 13.1 MeV can only be explained in terms of two overlapping levels having assignments of ($\text{5}\text{2}$, $\text{7}\text{2}$)^? and ($\text{3}\text{2}$, $\text{5}\text{2}$, $\text{7}\text{2}$)⁺.     

Electrical transport and magnetic properties of Nd2(WO4)3

Measurements of the molar magnetic susceptibility (X_m) of a powdered sample of Nd₂(WO₄)₃ in the temperature range 300–900 K, and the electrical conductivity (σ) and dielectric constant (?$\text{)}\text{?}$ of pressed pellets of the compound in the temperature range 4.2–1180 K are reported. X_m obeys the Curie-Weiss law with a Curie constant C= 3.13 K/mole, a paramagnetic Curie temperature θ= ?60 K and a moment of Bohr magnetons, p= 3.49 for the Nd³⁺ ion. The electrical conductivity data can be explained in terms of the usual band model and impurity levels. Both the σ and ?$\text{\$}\text{?}$data indicate some sort of phase transition round 1025 K. The conductivity follows Mott's law $\text{σ = A exp (?B/T}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{)}$ in the temperature range $\text{200 < T < 3000}\text{K with}\text{B = 45.00 (}\text{K}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{and}\text{A = 1.38 × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$. The dielectric constant increases slowly up to 600 K, as is usual for ionic solids. The increase becomes much faster above 600 K, which is attributed to space-charge polarization of thermally generated charge carriers.     

A Mössbauer study of amorphous Fe40Ni40B20

Amorphous Fe₄₀Ni₄₀B₂₀ (VITROVAC 0040) alloy has been investigated using ⁵⁷Fe Mössbauer Spectroscopy. The Curie temperature T_c is found to be well defined and is 695 ± 1 K. The quadrupole splitting just above T_c is 0.64 mm sec^?1. The crystallization temperature is 698 ± 2 K, close to but definitely above T_c. The average hyperfine field H_eff(T) of the glassy state shows a temperature dependence of $\text{H}{}_{\mathrm{<mtext>eff</mtext>}}\text{(0)[1 ? B}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{(T/T}{}_{\mathrm{c}}\text{)}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{? C}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{(T/T}{}_{\mathrm{c}}\text{)}{}^{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{? …]}$ indicative of the existence of spin wave excitations. The values of $\text{B}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{C}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ are found to be 0.40 and 0.06, respectively, for T/T_c ? 0.72. At temperatures close to T_c, H_eff(T) varies as (1 ? T/T_c)^β where β is one of the critical exponents and its value is found to be 0.29 ± 0.02.     

Hydrogen burning of 20Ne and 22Ne in stars

The ²⁰Ne(p, γ)²¹Na capture reaction has been studied in the energy range E_p = 0.37–2.10 MeV. Direct-capture transitions to the $\text{332 (}\text{5}\text{2}{}^{\mathrm{+}}\text{)}\text{and}\text{2425}\text{keV}\text{(}\text{1}\text{2}{}^{\mathrm{+}}\text{)}$ states have been found with spectroscopic factors of C²S(1d) = 0.77±0.13 and C²S(2s) = 0.90±0.12, respectively. The high-energy tail of the 2425 keV state, bound by 7 keV against proton decay, has also been observed in the above energy range as a subthreshold resonance. The excitation function for this tail is consistent with a single-level Breit-Wigner shape for a γ-width of Γ_γ = 0.31±0.07 eV at E_x = 2425 keV. The extrapolation of these data to stellar energies gives an astrophysical S-factor of S(0) = 3500 keV · b. Two new resonances at E_p = 384±5 and 417± 5 keV have been observed with strengths of ωγ = 0.11±0.02 and 0.06±0.01 meV, corresponding to the known states at and 2829 keV (presumably $\text{9}\text{2}{}^{\mathrm{+}}$), respectively. For the known E_p = 1830 keV resonance, a strength of ωγ = 1.0± 0.3 eV and a total width of Γ = 180± 15 keV were found. Branching ratios as well as transition strengths have been obtained for these three states. The Q-value for the ²⁰Ne(p, γ)²¹Na reaction (Q = 2432.3 ± 0.5 keV) as well as excitation energies for many low-lying states in ²¹Na have been measured. No evidence was found for the existence of the state reported at E_x = 4308±4 keV.In the case of ²²Ne(p, γ)²³Na, direct-capture transitions to six final bound states have been observed revealing sizeable spectroscopic factors for these states. The astrophysical S-factor extrapolated from these data to stellar energies, is S(0) = 67 ± 12 keV · b.The astrophysical as well as the nuclear structure aspects of the present results are discussed.     

Heat capacity of a five-coordinated ferromagnet,chloro bis(N,N-diethyldithiocarbamato)iron(III), in the temperature range from 0.4 to 20 K

The heat capacity of polycrystalline Fe[S₂CN(C₂H₅)₂]₂Cl has been measured in the temperature range from 0.411 to 19.55 K. The transition between ferromagnetic and paramagnetic states is characterized by a sharp λ-type anomaly centered at the Curie temperature, T_c = 2.412 ± 0.008 K. The enthalpy and the entropy of transition are 40.475 J mol^?1 and 11.199 J K^?1mol^?1 (= 1.347 R), respectively. The transition entropy is only 2.81% smaller than R In 4. This fact ascertains that the spin manifold is really a quartet. The ground spin states of the present compound are characterized by a zero-field splitting of the $\text{S =}\text{3}\text{2}$ state into two Kramers' doublets. The overlapping non-cooperative Schottky-type anomaly due to the energy separation between the two Kramers' doublets is separated tentatively from the cooperative heat capacity due to the exchange interaction. Based on a careful analysis of the transition entropy it may be concluded that the magnetic structure of the present complex would be a two-dimensional triangular Ising lattice. The exchange and the Curie-Weiss constants are also determined to be 0.155 and 4.19 K, respectively.     

Electron spin resonance investigation of the structural phase transitions in Alurea6(ClO4)3 and Ga urea6(ClO4)3

Second order structural phase transitions in Alur₆(ClO₄)₃ and Gaur₆(ClO₄)₃ with T_c ～ 300 K are studied by means of ESR on single crystals doped with the analogous Cr(III) compound. The transitions are antiferrodistortive and of the displacive type, the displacements resulting from the condensation of a X₂ mode $\text{(k = (0}\text{1}\text{2}\text{1}\text{2}\text{))}$ of the ClO₄ ions. The ESR parameters have the same temperature dependence as the order parameters and can be described by D and E～φ～. The space group describing the structure changes from S₆² to S₂¹, and the number of domains is multiplied by three. Above 300 K the crystals already consist of two domains, resulting from a ferrodistortive phase transition D_3d⁶ → S₆². The actual transition temperature of the latter phase transition lies at some temperature above the decomposition temperature of the crystals.