Critical slowing down of fluctuations in squaric acid (H2C4O4) at the phase transition observed by 13C spin-lattice relaxation

Spin lattice relaxation T₁ of naturally abundant ¹³C nuclei in squaric acid was measured close to the antiferroelectric-paraelectric phase transition temperature T_c = 373 K. A rapid increase in $\text{1}\text{T}{}_1$ is observed close to T_c coming from above, which follows the power law $\text{1}\text{T}{}_1\text{～ ε}{}^{\mathrm{?1.4}}$ where $\text{ε =}\text{(T ? T}{}_{\mathrm{c}}\text{)}\text{T}{}_{\mathrm{c}}$. This behaviour is explained on the basis of the two-dimensional character of the fluctuations.     

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.     

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.     

Nuclear spin-lattice relaxation of Co59 in CoB

We report the result of the Co⁵⁹ nuclear spin-lattice relaxation time T₁ measurements in the diamagnetic monoboride CoB. The analysis of the data, in the 4.2–300 K temperature range, allows us to separate three contributions to the relaxation rate: first a Korringa process, (T_1KT)^?1= 0.21 sec^?1K^?1 (in good agreement with the temperature independent isotropic Knight shift) from which we deduced the Co⁵⁹ hyperfine constant A=6.2 ×10^?6eV, second an impurity contribution independent of temperature and third a quadrupolar term, $\text{T}{}^{\mathrm{?1}}{}_{\mathrm{1Q}}\text{=3560 (}\text{T}\text{θ}{}_{\mathrm{D}}\text{)}{}^2\text{E(}\text{T}\text{θ}{}_{\mathrm{D}}\text{) sec}{}^{\mathrm{?1}}$, which is predominant at high temperature and well explained by the Van Kranendonk theory. It seems that it was the first time that such a quadrupolar effect was detected in a metallic compound. A remarkable coherency between Lundquist's three bands model and our experimental results has to be noted.     

Study on vacancy motion in Y2O3-doped CeO2 by 17O NMR technique

The ¹⁷O NMR measurement was made to elucidate the microscopic nature of vacancy motion in Y₂O₃-doped CeO₂. Spin-lattice relaxation rate, T^?1₁, spin-spin relaxation rate, T^?1₂, and resonance intensity were measured at v₀ = 8.13 MHz as a function of temperature [385 < T (K) < 1110] and composition [$\text{0.06 <}\text{Y}{}_2\text{O}{}_3\text{(}\text{m}\text{o}\text{) < 6}$]. The static electric field gradient associated with lattice defects resulted in the composition dependences of the line width and the intensity. In low dopant concentrations, doubly peaked temperature dependence of T^?1₁ was found, while a single and asymmetric peak was observed in high concentrations. T^?1₁ of 4.0 and 6.0 $\text{m}\text{o}$ doped samples were analyzed using a barrier height distribution model for the oxygen vacancy jump. The mean value of the activation energy was found to increase with the Y₂O₃ concentration.     

Strengths and lorentz broadening coefficients for spectral lines in the ν3 and ν2 + ν4 bands of 12CH4 and 13CH4

Line strengths and self- and nitrogen-broadened half-widths were measured for spectral lines in the ν₃ and ν₂ + ν₄ bands of ¹²CH₄ and ¹³CH₄ from 2870–2883 cm^?1 using a tunable diode laser spectrometer. From measurements made over a temperature range from 215 to 297 K, on samples of ¹²CH₄ broadened with N₂, we deduced that the average temperature coefficients n, defined as $\text{b}{}_{\mathrm{<mtext>L</mtext>}}{}^0\text{(T) = b}{}_{\mathrm{<mtext>L</mtext>}}{}^0\text{(T}{}_0\text{)(}\text{T}\text{T}{}_0\text{)}{}^{\mathrm{?n}}$, of the Lorentz broadening coefficients for the ν₃ and ν₂ + ν₄ bands of ¹²CH₄ were 0.97 ± 0.03 and 0.89 ± 0.04, respectively. A smaller increase is observed in line half-width with increasing pressure for E-species lines, for both self- and nitrogen-broadening, than for other symmetry species lines over the range of pressures measured, 70 to 100 Torr.     

Magnetic circular dichroism of transition metal ions in solids—II K2NaGaF6: Cr3+

The absorption and MCD spectra of the ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{a}}$ and ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{b}}$ spin-allowed transitions of Cr³⁺ in K₂NaGaF₆ are reported. It is shown that transitions to the ${}^4\text{T}{}_{\mathrm{1g}}$. states are induced by T_1u vibratio the other spin-allowed transition, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, there are three competing intensity mechanisms: electric dipole induced by T_1u vibrations, electric dipole induced by T_2u vibrations and magnetic dipole, and an estimate is made of the relative importance of these. The magnetic dipole ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^2\text{E}{}_{\mathrm{g}}$ zero-phonon line is observed to be accompanied by a vibrational sideband for which the coupling is predominantly with T_2u vibrations. Other weak transitions are observed in MCD spectra and their origin briefly discussed.     

Long-lived non-equilibrium population of Fe3+ electronic states after the K-capture of 57Co

Mössbauer emission spectra of a frozen aqueous solution of ⁵⁷CoCl₂ show contributions from the $\text{S}{}_{\mathrm{z}}\text{= +}\text{5}\text{2}$ and the $\text{S}{}_{\mathrm{z}}\text{= +}\text{3}\text{2}$ Zeeman levels of Fe³⁺ ions at T = 4.2 K in H ? 30 kG. The K-capture results in a non-equilibrium state of relaxation time comparable to the lifetime of the nuclear excited state (～ 10^?7 s).     

Spectroscopic investigation of [(NH4)xK1−x]2SnCl6 mixed crystals

Polycrystalline samples of the solid solution [(NH₄)_xK_1?x]₂SnCl₆(0?x? 1) have been investigated by DSC, X-ray diffraction and Raman scattering experiments. Substitution of K⁺ by NH⁺₄ depresses the phase transition temperature T₁. For 0? x ?0.05 a linear temperature coefficient $\text{d}\text{T}{}_1\text{dx=?5.16}\text{K/mol}$ % is obtained. The cubic lattice constant roughly obeys Vegard's law, whereas the linewidth of the SnCl₆^2?F_2g internal vibration displays a nonlinear dependence on composition.     

Study by brillouin scattering of the C33 constant of thiourea submitted to an electric field

The C₃₃ constant is discontinuous for the lock-in transition at T₁ = 169 K. The variation ΔT₁ of the temperature of transition is a linear function of the applied electric field E and we find $\text{d}\text{T}{}_1\text{d}\text{E}\text{=0.82 deg.cm kV}{}^{\mathrm{?1}}$.Above a mean field E = 10 kV cm^?1 the transition observed for a first heating spreads on several degrees because damages appear in the incommensurate phase and the electric field becomes inhomogeneous.The results obtained at low fields are in very good accordance with the value of $\text{d}\text{T}{}_1\text{d}\text{E}$ calculated from the Clapeyron formula.Taking into account of the incommensurability of the phase above T₁, it can be shown that

$\text{dT}{}_1\text{dE}\text{=}\text{C}\text{2πP}{}_{\mathrm{o}}\text{3}\text{3}\text{?}\text{2}$

The knowledge of the spontaneous polarisation P₀ gives for the Curie constant C = 2.1 × 10³ K in qualitative agreement with the value deduced from measurements of the dielectric constant in the ferroelectric direction.     

Jahn-Teller analysis of the 3T1(P) absorption band of Ni2+ in GaP

Comparison between experimental absorption due to the ${}^3\text{T}{}_1\text{(F)?}{}^3\text{T}{}_1\text{(P)}$ transition of substitutional Ni²⁺(d⁸) in GaP and theoretical predictions based on the Jahn-Teller model is presented. Numerical solution of the Hamiltonian, in which spin-orbit interaction and T₂-mode Jahn-Teller coupling are included, is in very good agreement with the energy position and intensities of the observed absorption lines.     

Electron paramagnetic resonance of 61Ni+ in CuGaS2

EPR of ⁶¹Ni⁺ doped CuGaS₂ at 4.2 K leads to the following experimental data: $\text{g = 1.918 ± 0.006 A  < 12 × 10}{}^{-4}\text{cm}{}^{-1}\text{, g}{}_{\mathrm{\perp }}\text{= 2.328±0.006 A}{}_{\mathrm{\perp }}\text{= (65±2) × 10}{}^{-4}\text{cm}{}^{-1}$. High axial field splitting of ²T₂ state stabilizes the center against Jahn-Teller interaction. Covalency reduction factor k is 0.76.     

Study of 11B at high excitations with the 9Be(3He,p)11B and 9Be(α, d)11B reactions

The nucleus ¹¹B has been studied over the excitation energy range from 8.5 MeV to 21.5 MeV with the ⁹Be(³He, p)¹¹B / reaction at / E_{³He = 38 MeV}. The analogs of the parent states in ¹¹Be have been located at 12.56, 12.92, 14.40, 16.44, 17.69, 18.0, 19.15 and 21.27 MeV. A complementary measurement with the ⁹Be(α, d)¹¹B reaction at E_α = 48 MeV demonstrates that the 16.44, 17.69, 18.0 and 19.15 MeV resonances have rather pure isospin $\text{T}{}_{\mathrm{f}}\text{=}\text{3}\text{2}$. The 14.40 MeV state is a strongly isospin-mixed analog of the $\text{5}\text{2}{}^{\mathrm{+}}\text{1.78}\text{MeV}$ state in ¹¹Be. It is argued that spin S = 1 transfer is involved in the excitation of the 16.44 MeV state and its 3.887 MeV parent in ¹¹Be in a two-step stripping process. The $\text{T}{}_{\mathrm{f}}\text{=}\text{1}\text{2}$ states and the lowest three $\text{T}{}_{\mathrm{f}}\text{=}\text{3}\text{2}$ states are compared with the predictions of DWBA utilizing shell-model form factors. It is concluded that the $\text{T}{}_{\mathrm{f}}\text{=}\text{1}\text{2}$ strength is more strongly fragmented than is implied by the calculations of Teeters and Kurath.     

Ni2+ emission in MgO,KMgF3, KZnF3 and MgF2

The emission of Ni²⁺ ions in MgO, KMgF₃, KZnF₃ and MgF₂ crystals has been investigated. The fine structure on the bands at about 20 000 cm^-1 and 13 000 cm^-1 has been studied in detail and from this and the excitation spectra these bands are assigned to ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{A}{}_{\mathrm{2g}}$ and ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{T}{}_{\mathrm{2g}}$ transitions respectively.     

Further neighbour interactions in the quasi b.c.c. Heisenberg ferromagnets M2 Cu X4 · 2H2 O (M = NH4, K,Rb or Cs; X = Cl or Br)

The Curie-Weiss constant θ of the quasi b.c.c., $\text{S =}\text{1}\text{2}$, Heisenberg ferromagnets, (NH₄)₂ Cu Br₄ · 2H₂ O and Rb₂ Cu Br₄ · 2H₂ O, have been derived from measurements of the susceptibility in the paramagnetic region (4.2 < T < 100 K) and of the high-field magnetization curves at $\text{T = 4.2}\text{K}\text{(}\text{T}\text{T}{}_{\mathrm{c}}\text{? 2.3)}$. The $\text{T}{}_{\mathrm{c}}\text{θ}$ values obtained point to the presence of further neighbour interactions considerably stronger than previously assumed. The effective number of equivalently interacting magnetic neighbours is estimated to be at least seventeen.     

The 5T2g → 5Eg absorption in MgO: Fe2+

At helium temperatures two sharp lines at 9350 and 9510 cm^?1 have been observed for the first tune on the low-energy side of the broad double-peaked absorption corresponding to the ${}^5\text{T}{}_{\mathrm{2g}}\text{→}{}^5\text{E}{}_{\mathrm{g}}$ transition in Fe²⁺ at the octahedral site in MgO. The lower energy line has a half width of 4 cm^?1; Zeeman measurements show that it is of magnetic dipole origin. The Zeeman spectra are consistent with those expected for a pure electronic transition from the (⁵T_2g)T_2g ground state to the ⁵E_g excited state. The second line, with a halfwidth of ~ 35 cm^?1, a vibrational sideband.     

Structure magnetique en champ applique nul de l'acetate de manganese tetrahydrate Mn(CH3COO)2, 4H2O

The magnetic structure of manganous acetate Mn(CH₃COO)₂, 4H₂O has been solved by neutron diffraction. Manganous acetate crystallizes in the space group $\text{P2}{}_1\text{c}$ with Z = 6. Manganese atoms (in position 2a and 4e) are located in (100) planes. Below T_N = 3.18 K this compound is antiferromagnetic in a zero applied field with the k vector [$\text{1}\text{2}$ 00]. The plane (100) is ferromagnetic. The magnetic group is $\text{P}{}_{\mathrm{2a}}\text{2}{}_1\text{c}$.     

Study of the 58Ni(τ, α)57Ni reaction at 25 MeV

The ⁵⁸Ni(τ, α)⁵⁷Ni reaction has been studied at 25 MeV incident energy. Angular distributions have been measured from 5° to 50° with a split-pole spectrometer up to 13.5 MeV excitation energy. A local zero-range DWBA analysis has been carried out, allowing l-assignments for about eighty levels, most of them previously unknown. An isospin-dependent potential has been used in the calculation of the neutron form factor for both T_<and T_> states, and the C²S values deduced using this procedure are compared to those obtained with the usual separation energy method. Analog states of eleven ⁵⁷Co levels have been identified and the eventuality for isospin mixing in ⁵⁷Ni has been discussed. A sum rule analysis has been carried out and energy centroids of hole states have been determined. About 60% of the $\text{1}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{and}\text{2}\text{s}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{T}{}_{\mathrm{<}}$ strengths and the full $\text{1}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{1}\text{f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ hole strengths are observed. It is shown that the two excess neutrons in the ⁵⁸Ni ground state mainly populate the $\text{2}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{, 1}\text{f}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{and}\text{2}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ orbitals, whereas the occupancy number of the $\text{1}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ subshell is found to be smaller than 0.1%. Some non-pickup angular distributions have also been observed and a CRC analysis assuming two-step processes in the (τ, α) reaction and weak-coupling wave functions for final states has been attempted. Assignments of J^π values are proposed for four ⁵⁷Ni levels, based on this analysis.     

Electron spin relaxation of irradiated ferroelectric KDP: K2SeO4

Electron spin resonance relaxation times were measured for the radiation induced radical ion SeO₄^3? in selenium doped KDP single crystals. The spin-lattice relaxation time was found to obey the relation $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>R</mtext>}}{}^{\mathrm{?1}}\text{= AT + BT}{}^5\text{∫}{}_0{}^{\mathrm{<mtext>\theta </mtext><mtext>2T</mtext>}}\text{x}{}^4\text{csch}{}^2\text{x}\text{d}\text{x}$ from 7 K to 200 K except in the neighborhood of the transition temperature where the data fit the expression T₁^?1 = T_1R^?1b_±T ? T_c^m± where θ is the Debye temperature and the plus and minus signs refer to data at temperatures above and below T_c respectively.     

Formation and lithuim ionic conduction of the antifluorite type solid electrolytes,Li2+x-y-z[(NH)1-x-y-zNxClyHz]

Antifluorite type solid electrolytes, Li_2+x-y-z[(NH)_1-x-y-zN_xCl_yH_z] have been synthesized from Li₃N, LiCl and LiCl·H₂O or $\text{Li}{}_2\text{[(}\text{NH}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{N}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{H}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}$]. Either of the last two compounds introduces NH^2- ions into the product and is indispensable to form the antifluorite type structure. The lattice parameter decreases with increasing amount of NH^2- ions in the compound, reflecting the difference of anion sizes between Cl^- and NH^2- ions. Activation energies of Li⁺ diffusive motion, derived from both conductivity and NMR measurements, increase with concentration of NH^2- ions, although the values differ by a factor of ≈2 netween the both methods.