The bonded water molecule3ĪII: 180° Flips and diffusion

The proton spin-lattice relaxation time, T₁, is measured as a function of temperature in α -(COOH)₂·-2H₂O, K₂HgCl₄· H₂O and LiCHO·H₂O. The relaxation is caused by 180° flips of the water molecules about their 2-fold axes and good agreement is obtained between calculated and observed values of T₁. Empiricly the flip rate follows a classical Arrhenius equation: P· exp $\text{(? ΔH}\text{(RT))}$. A literature survey of values of P and ΔH obtained from similar investigations on other hydrates is given. The survey shows that the preexponential factor, P, is a function of the activation enthalpy, ΔH. P increases from 10¹² to 10¹⁷ Hz when ΔH changes from 2 to 17 $\text{kcal}\text{mole}$. Using a dynamical rate theory as formulated by Feit, we find the flip rate is given by: K₂· √(ΔH)· exp (K₁ΔH)· exp $\text{(?ΔH}\text{(RT>))}$. This expression can be fitted to the observed data using K₁ = 0.69 $\text{mole}\text{kcal}$ and K₂ = 2 × 10¹¹ Hz · $\text{(kcal}\text{mole)}$$\text{?1}\text{2}$. Thus both the frequency factor, K₂√ (ΔH), and the entropic factor, exp (K₁ΔH), have been obtained for flipping water molecules in hydrates. The values of K₁ and K₂ are shown to be physically reasonable.     

Raman study of charge-density-wave phase transition in quasi-one-dimensional conductor (TaSe4)2I

Polarized Raman spectra were obtained in the quasi-one-dimensional conductor (TaSe₄)₂I above and below the charge-density-wave (CDW) transition temperature (T_c=263 K). The Raman intensities of many peaks become intenser and two of the phonon peaks shift to higher frequency with decreasing temperature. Moreover a new broad peak at about 90 cm^?1 and a new peak around 166 cm^?1 appear in the low-temperature phase. The polarization characteristic shows that the former is assigned to totally symmetric mode. The damping constant of the phonon at 90 cm^?1 increases markedly with increasing temperature. The frequency shifts to higher frequency as the temperature increases and the coupling coefficient is approximately proportional to (T_c?T)^{$\text{1}\text{2}$}. This peak becomes Raman active owing to the CDW phase transition. The temperature dependence of the damping constant and the frequency shift may have a relation to the dynamical properties of the CDW phase transition.     

Electrical resistance and magnetoresistance of amorphous alloys Gd67Co33 and Pd80Si20

In search for structural contributions to the low temperature anomaly we report high resolution resistance and magnetoresistance measurements ($\text{0.02}\text{K}\text{? T ? 20}\text{K}$) of amorphous splats of Gd₆₇Co₃₃ and Pd₈₀Si₂₀. For both alloys, the resistivity ?(H = 0, T) has a minimum at T ～ 10 K and increases with decreasing T. The ferromagnetic Gd₆₇Co₃₃ shows a strong negative field dependence of $\text{Δ?}\text{?(0)}$, saturating at H ～ 2T for T = 4.2 K but no measurable change in $\text{??}\text{?}\text{T}$ below 10 K is observed.The diamagnetic Pd₈₀Si₂₀ exhibits a positive field dependent magnetoresistance $\text{[Δ?}\text{?(0)]}\text{(}\text{H}\text{)}$ at low temperatures. Additionally, a field dependent part in $\text{??}\text{?}\text{T}$ is found which is probably due to paramagnetic impurities (～ 1 ppm Fe). However, there is also a field independent contribution in the amorphous state of Pd₈₀Si₂₀, which vanishes after crystallization. We attribute this to non-magnetic scattering induced by the disordered structure.     

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.     

Magnetic field dependent optical dephasing in LaF3:Er3+

Optical dephasing of the 5388 Å transition between the lowest Kramers doublets of the ⁴S_{$\text{3}\text{2}$} and ⁴I_{$\text{15}\text{2}$} multiplets of Er³⁺:LaF₃ has been studied by photon echo, optical phase switching and optical free induction decay. Er³⁺?¹⁹F hyperfine interactions produce dephasing which is two orders of magnitude faster than in previously studied non-Kramers systems, but at high field changes in the spin dynamics result in microsecond dephasing. For the lower Zeeman component of ⁴S_{$\text{3}\text{2}$}, T₂ (=6μs) is independent of H₀ whereas for the upper component the dephasing is rapid and strongly field dependent. This is quantitatively accounted for by spin lattice relaxation of the upper component of ⁴S_{$\text{3}\text{2}$}. Below 20 kG concentration and temperature dependent dephasing due to electron spin diffusion is observed.     

Coupled mode behavior of the soft E(TO) phonon of Pb(Ti1-x,Zrx)O3 and (Pb1-3x2, Lax)TiO3

We report the temperature dependence of the low frequency part (ω < 100 cm^?1) of the Raman spectra of the Pb(Ti_1-x, Zr_x)O₃ and $\text{(}\text{Pb}{}_{\mathrm{<mtext>1-</mtext><mtext>3x</mtext><mtext>2</mtext>}}$, La_x)TiO₃ systems. The spectra indicate a coupled mode behavior between the soft E(TO) phonon and a mode which produces an additional band in the spectra. We discuss the possibility that the additional band might be due to zone boundary tranverse acoustical phonons which couple to the q ～ 0 soft E(TO) mode because of the disorder existing in the systems.     

NMR investigation of the structure of NiZrF6·.6H2O at low temperatures

Previous studies have shown that NiZrF₆.6H₂O can be described by an axial spin Hamiltonian with parameters g = 2.33 and $\text{D}\text{k}\text{= ?3.14}\text{K}$, and exhibits ferromagnetic ordering at T_c = 164mK. Our room temperature X-ray measurements confirm that NiZrF₆·.6H₂O is isomorphous with NiSnCl₆·.6H₂O and give lattice parameters of $\text{a = 6.55}\text{A}\text{?}$ and α = 96°09′. Proton NMR measurements show that there exist important molecular motions at room temperature and that the space group remains $\text{R}\text{3}$ down to liquid helium temperatures. The positions of all twelve protons have been determined and are found to lie on a sphere of radius 2.9 Å centered on the nickel ion.     

Softening of acoustic and optical modes in ferroelastic phase in Hg2Br2

The softening of an acoustic and an optical phonons in Hg₂Br₂ has been investigated by means of the light scattering technique.It has been observed that the cube of the frequency of the soft optical phonon varies proportionally with the temperature below T_c.An expression for the relation of the elastic constant C₆₆ to the temperature has been derived from the phenomenological thermodynamic potential function. The observed temperature dependence of the elastic constant and the optical phonon frequency is described when we assume that the order parameter Q varies as $\text{Q ∝ [T ? T}{}_0\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>6</mtext>}}$.     

Specific heat of some phosphate compounds

Specific heats C^E_p of some phosphates have been measured on powder samples, in the temperature range 100–373 K. Anomalous behaviour of C^E_p (T) has been observed for Co(H₂PO₄)₂$\text{s}\text{?}$ 2H₃PO₄ and Mn(H₂PO₄)₂ 2H₃PO₄ around 190 K. In triclinic Ba(H₂PO₄)₂ a phase transition was found at about 147 K, i.e. at a somewhat higher temperature than according to previous dielectric measurements.     

A light scattering investigation of the incommensurate transition in BaMnF4

The results of a Brillouin scattering investigation of BaMnF₄ near its incommensurate structural phase transition at T_i=247 K are reported. We have observed an anomalous dynamic central peak in the polarized (bb) spectrum, with $\text{q}\text{6}\text{c}$. This feature is visible only very near T_i, and possesses a width which is strongly wavevector dependent. The indicated behavior is Λ=D_tq², with D_t=0.14 ± 0.02 cm²sec^-1. It is identified as the result of a coupling between the LA phonon and the soft mode, where the latter contains a relaxing self energy due to a linear coupling to a diffusive process, possibly entropy fluctuations. The narrow central peak is not visible for $\text{q}\text{6}\text{a}$. In addition, we report an anomalous dispersion (～4%), in the LA mode propagating along $\text{c}$ (V_cc) near T_i.     

Electrical transport properties of a quasi-one-dimensional Nb3Te4 single crystal

The electrical resistance of a linear chain metal Nb₃Te₄ were measured from 1.3 to 320 K. The residual resistance ratio $\text{R(300}\text{K}\text{)}\text{R(4.2}\text{K}\text{)}$ is about 3. Nb₃Te₄ shows an anomaly in the resistivity vs temperature at about 80 K, suggesting an occurrence of a charge-density-wave transition. The transverse and longitudinal magnetoresistance at 4.2 K are proportional to the magnetic field in the range of 2–58 kOe. In the superconducting region close to the transition temperature T_c, the critical magnetic field H_c2 is proportional to δT=T_c?T. The angular dependence of H_c2 fits well with the fluxoid model of the Ginzburg-Landau theory. The ratio of the critical fields parallel and perpendicular to the chain direction is 4.8.     

TA1[110] phonon dispersion and martensitic phase transition in ordered alloys Fe3Pt

In a previous neutron scattering study, we had observed that the TA phonon softening in L1₂-ordered ferromagnetic Fe₇₂Pt₂₈ Invar is pronounced at the zone boundary M-point and leads to an antiferrodistortive phase transition at low temperatures. Here, we report on similar neutron scattering investigations on two ordered crystals with higher Fe content to investigate the relation between the TA phonon softening and the martensitic transformation, which occurs in Fe-rich ordered Fe-Pt. We find that the TA phonon softening, especially at the M-point zone boundary, does not depend on the composition of the investigated crystals. In Fe_74.5Pt_25.5, however, the antiferrodistortive phase transition temperature is enhanced due to tetragonal strain preceding the martensitic transition. In Fe₇₇Pt₂₃ a precursor driven premartensitic phase transition is not observed. The structure of the martensite is, however, influenced by the soft mode lattice instability of the austenite. This would explain the origin of structural details found previously for Fe₃Pt thermoelastic martensite. Received 18 January 1999 and Received in final form 11 March 1999     

Magnetocrystalline anisotropy in FeNi invar alloys under high magnetic fields

Torque measurements were made for FeNi Invar alloys at 4.2 K in high magnetic fields up to 47 kOe by using a split pair type superconducting magnet. It was found that the magnetocrystalline anisotropy constant, K₁, determined from the observed torque curves increases monotonically with increasing the field. The increasing rate, $\text{d}\text{K}{}_1\text{d}\text{H}$, was extraordinally high and could not be explained by simply considering the Zener's power law. It was suggested that some other terms, such as the Fermi-level dependent one, play an important role in this quantity.     

ΔK = 2 transitions in H2CO and D2CO

Weak transitions of the type ΔJ = ± 1, $\text{Δ}\text{K}{}_{\mathrm{a}}\text{= ? 2}$, ΔK_c = ± 3 have been observed in H₂CO and D₂CO by the millimeterwave double resonance method and also by direct absorption with a Stark modulated spectrometer. The addition of these new transitions in a least-squares analysis, in which all previously known microwave and millimeterwave data are also included, results in an improved set of rotational and distortion constants.     

A neutron diffraction study of structural changes in one-dimensional K2Pt(CN)4Br0.3 · 3H2O from 77–323°K

Single crystal neutron diffraction measurements of K₂Pt(CN)₄Br_0.3 · 3H₂O (KCP) above room temperature, to the point of irreversible crystal breakdown (318–323°K), and at liquid nitrogen temperature (77°K), give no indication of a crystallographic phase change. Full three-dimensional data collected at 77°K ($\text{a = 9.848(5)}\text{A}\text{?}\text{, c = 5.714(3)}\text{A}\text{?}\text{,}\text{and space group}\text{P4mm}$) indicate that the structure is essentially unchanged from that at room temperature except for increased hydrogen bonding association between H₂O(2) and Br(1). The possible relationship between the hydrogen bonding changes and Br(1) site ordering is discussed.     

A study of some potassium hexachlorometallate complexes using electron spectroscopy

X-ray photoelectron (ESCA) spectra of the core (Cl 2p K 2p and metal 4f, if present) and valence orbitals are reported for K₂ReCl₆, K₂OsCl₆, K₂IrCl₆· 3 H₂O, K₂PtCl₆, K₃MoCl₆, and K₂SnCl₆. The K 2p_{$\text{3}\text{2}$} binding energy was found to be nearly constant (292.7 eV) and that of Cl to increase very slightly with increasing atomic number for the third row transition metals. The chemical shifts of Re(IV), Os(IV), Ir(IV), and Pt(IV) relative to the metals were in qualitative agreement with atomic calculations utilizing configurations obtained from extended Hückel calculations. The valence spectra of the transition metal complexes exhibit a three-band structure. On the basis of MO results and intensity considerations the high binding energy band is assigned as a composite of the a_1g, e_g, 1t_2g MO's. The middle band represents the t_2u, 2t_1g MO's; and the low binding energy band the 2t_2g MO. Calculated nd orbital photoionization cross sections correlate reasonably well with the relative intensifies of the valence manifolds. Comparison of band separations and charge-transfer transition energies suggests that interelectronic repulsion and MO energy separation contribute about equally to the overall charge-transfer energy.     

Etude comparative des structures des alumines β stoechiometrique et non stoechiometrique: Transition de phase dans l'alumine β stoechiometrique (II)

The usual preparation methods of β alumina lead to a non stoichiometric compound $\text{(β“N.S.”)}$ of formula 11Al₂O₃?(1 + x) B₂O with x ≈-0.3; a metastable phase with a composition close to stoichiometry $\text{(β“S”}\text{and}\text{x ? 0)}$ can however also be obtained. X-Ray diffuse scattering studies of this stoichiometric form of silver β alumina reveals a sharp order—disorder phase transition at about 307 K. The low temperature ordered state of the silver ions is found to correspond to a 3D hexagonal superstructure with the lattice constants $\text{a}\text{3}\text{, a}\text{3}\text{, c}$. Above the transition temperature 3D short range order is observed up to about 315 K, where a cross over occurs towards a higher temperature 2D short range state, similar to that previously observed at low temperature in $\text{β}{}_{\mathrm{<mtext>Ag</mtext>}}\text{“N.S.”}$. Above 500 K the conducting silver ions are found to be in a 2D quasi liquid state. A similar type of order—disorder phase transition seems to occur in stoichiometric sodium β alumina at lower temperature. It is concluded that the very particular behaviour namely the absence of phase transition in the usual forms of β alumina is a direct consequence of non stoichiometry.     

Charge-density wave instability and nonlinear transport in Tl0.3MoO3 a new blue molybdenum oxide bronze

Single crystals of Tl_0.3MoO₃ blue bronze were grown by the temperature gradient flux technique for the first time. Tl_0.3MoO₃ crystalizes with monoclinic symmetry, space group C2, C2/m or Cm, $\text{a = 18.486(1)}\text{A}\text{?}$, $\text{b = 7.5474(6)}\text{A}\text{?}$, $\text{c = 10.0347(7)}\text{A}\text{?}$, β = 118.377(6)° and appears to be isostructural with the K_0.3MoO₃ blue bronze. The physical properties of Tl_0.3MoO₃ are similar to those of the K₃MoO₃ and Rb₃MoO₃ phases. The resistivity of Tl_0.3MoO₃ is highly anisotropic and its temperature susceptibility (4.2–300K) decreases sharply with decreasing temperature near the transition seen in the resistivity. The onset of another transition <60K is also indicated by the susceptibility data. Non-linear current-voltage (I–V) characteristics observed at ～70K above applied threshold voltages of the order of ～300mV/cm suggest the sliding of charge density condensate.     

Anomalous properties of crystals with ferroelectric phase transition induced by off-center ions

It is given the theoretical study of some properties of strongly polarizable dielectric crystals in which off-center impurity ions induce ferroelectric phase transition. The spontaneous polarization, transition temperature, soft mode frequency, dielectric susceptibility, ultrasonic attenuation, nuclear spin-lattice relaxation are analyzed. The theory explains observed in K_1?xLi_xTaO₃ saturation of remanent polarization with off-center Li⁺ concentration increasing, close to $\text{x}$ dependence of phase transition temperature, the anisotropy of ultrasonic attenuation, the absence of anomalies of Li nuclear spin-lattice relaxation rate near T_c.