Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

The pressure influence on the incommensurate-commensurate ferroelectric phase transition in [4-NH2C5H4NH][SbCl4]

The dielectric properties of the [4-NH₂C₅H₄NH] SbCl₄ (abbreviated as 4-APCA) crystal were investigated under hydrostatic pressure up to 300 Mpa. The pressure-temperature phase diagram was given. The paraelectric-ferroelectric phase transition (II→III) temperature (T_c) increases linearly with increasing pressure with a slope dT_c/dp=21×10⁻² K/MPa. The pressure dependence of Curie-Weiss constants has been evaluated also. In the paraelectric phase (II) the Curie constant (C₊) was pressure dependent whereas the C₋ constant over the ferroelectric phase (III) was almost constant. The results are interpreted in terms of improper and displacive type phase transition model with a soft phonon at a zone boundary.     

Particle size dependence of exchange-bias and coercivity in CuO nanoparticles

For CuO nanocrystals of size 6.6-37 nm, the exchange bias H_eb and coercivity H_c are measured at 5 K in zero-field-cooled (ZFC) and field-cooled (FC at 50 kOe) samples and their variations investigated as a function of particle size D. The similar 1/D variations observed for the difference coercivity ΔH_c=H_c(FC)−H_c(ZFC) and the interfacial exchange energy Δσ=H_ebM_fD are discussed in terms of the ferromagnetic magnetization M_f being produced by the uncompensated surface Cu²⁺ spins in the otherwise antiferromagnetically ordered CuO nanoparticles. This leads to the observation that the experimentally measured ΔH_c provides a good measure of Δσ in nanoparticle systems, with H_eb/ΔH_c varying as 1/M_fD.     

Quasi-particle excitations around a pair of half-quantum vortices in p- wave superconductors

Triplet superconductors such as Sr₂RuO₄ and Na_xCoO₂⋅yH₂O are now found to be p-wave (p_x ± ip_y) or f-wave ((p_x ± ip_y) cos cp_z) superconductors. It was phenomenologically suggested that in these p-wave or f-wave superconductors, a pair of half-quantum vortices (HQVs) becomes stable. Using the Bogoliubov-de Gennes equation, previously we have analyzed quasi-particle excitations around an HQV at one end of a d-soliton for simplicity. In next study, we will investigate the stability of the pair of HQV’s, which are connected by the d-soliton. For this purpose, we have developed a new numerical method to solve the Bogoliubov-de Gennes equation for two vortices state, using Mathieu functions.     

Single crystal EPR and optical absorption study of Cr doped l-histidine hydrochloride monohydrate

EPR study of the Cr³⁺ ion doped l-histidine hydrochloride monohydrate single crystal is done at room temperature. Two magnetically inequivalent interstitial sites are observed. The hyperfine structure for Cr⁵³ isotope is also obtained. The zero field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations and the parameters are: D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.9108±0.0002, g_y=1.9791±0.0002, g_z=2.0389±0.0002, A_x=(252±2)×10⁻⁴ cm⁻¹, A_y=(254±2)×10⁻⁴ cm⁻¹, A_z=(304±2)×10⁻⁴ cm⁻¹ for site I and D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.8543±0.0002, g_y=1.9897±0.0002, g_z=2.0793±0.0002, A_x=(251±2)×10⁻⁴ cm⁻¹, A_y=(257±2)×10⁻⁴ cm⁻¹, A_z=(309±2)×10⁻⁴ cm⁻¹ for site II, respectively. The optical absorption studies of single crystals are also carried out at room temperature in the wavelength range 195-925 nm. Using EPR and optical data, different bonding parameters are calculated and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are: B=636, C=3123, Dq=2039 cm⁻¹, h=1.46 and k=0.21, respectively.     

An interpretation of published data on high-angle neutron elastic scattering in Tb metal

Published data of Steinsvoll et al. on high-angle elastic scattering of polarized neutrons by Tb metal are interpreted. States of the 4f-5d system at any one atomic site are assumed to be expressible as sums of products of 4f states ¦6M〉 with 5d states ¦d_M〉, where ¦6M〉 (M = 6, 5 or 4) denote 4f states with components M of their angular momenta along the b axis, and ¦d_M〉 denote 5d states which satisfy 〈d₆¦d₅〉 = β, 〈d₆¦d₄〉 = β². A small angle ? is introduced which represents an amount of tipping of the 4f moment away from the b axis which would occur if β = 1. The radii of 4f wave functions are allowed to increase by a small fraction s above values given by LS-averaged Dirac-Fock calculations. The quantities ?, βε, s and the effective polarization P of the neutron beam used are treated as adjustable parameters subject to β ? 1, and a fifth partially adjustable parameter subject to a constraint due to input information is introduced. A good fit to the results for eighteen scattering wave vectors q for which $\text{(}\text{q}\text{4π}\text{)>5nm}{}^{\mathrm{?1}}$ is obtained with ε=(10⁺⁴_?2)°, βε=(9±1)° and s=(0.018 ± 0.003).     

Synthesis and hydrolysis of octacalcium phosphate and its characterization by electron microscopy and X-ray diffraction

Octacalcium phosphate (OCP) powder was produced by precipitating 250 mL Ca(CH₃COO)₂ 0.04 M into 750 L of phosphate solution (5 mmol Na₂HPO₄ and 5 mmol NaH₂PO₄) at a constant temperature of 60 °C and pH 5, which resulted in a dry white powder. X-ray diffraction (XRD), transmission electron microscopy (TEM) analysis, and the electron diffraction pattern (SAED) all showed only OCP. Hydroxyapatite (HAP) was directly obtained through hydrolysis of the powder. The total transformation of OCP into HAP was registered over a period of 6 h. During the first 30 min of hydrolysis both phases coexisted. The two phases and the OCP-HAP interface were structurally analyzed through XRD and TEM. OCP parameters (calculated by the Rietveld method) are a=19.70, b=9.50, c=6.85 Å; α=90.03°, β=92.48°, γ=108.32° (triclinic P-1) with average crystal size of 13.5±0.2 nm, while HAP parameters were a=9.45, c=6.87 Å (hexagonal P6₃/m) with average crystal size of 16.9±0.2 nm.     

Investigation of the decay of charmed particles produced in neutrino interactions

The decay of charmed particles produced by high-energy neutrinos has been studied by an experiment using simultaneously emulsion, bubble chamber and counter techniques. Eight charmed particle candidates, 5 positively charged and 3 neutral, have been found in the emulsion, where their production and decay have been directly observed. One of these events is identified as a Λ_c⁺ baryon of mass 2.26±0.02 GeV/c² which undergoes the decay Λ_c⁺→pK^?π⁺ after a proper time of (7.3±0.1) · 10^?13 s.A statistical analysis of the other observed decays leads to the mean-life values τ⁺=(2.5_?1.1^+2.2) · 10^?13 s, τ⁰=(0.53_?0.25^+0.57) · 10^?13 s, for the sample of charged particles enriched by a similar event found in a previous experiment, and for the sample of 3 neutral particles, respectively. The former value is only slightly affected by including in the sample the Λ_c⁺ event or excluding that of the previous experiment.     

Proximity effect in the finite and incommensurate ferromagnet/superconductor systems

The original theory of a proximity effect is proposed for the bi- and tri-layered system ferromagnetic metal/superconductor (F/S) in dirty limit. The F₁/S/F₂ trilayer is examined more closely. The distinctions in materials, in thicknesses of F layers (d_f1 and d_f2), in parameters interfaces, and in local environments of layers are considered among the causes of incommensurability of trilayer. The peculiar T_c(d_f1, d_f2) interference pattern is predicted for the F₁/S/F₂ systems. The reentrant superconductivity and possibility of the better observability of the spin-valve regime are discussed.     

Optical properties of natural quantum-well compounds (C6H5-CnH2n-NH3)2PbBr4 (n=1-4)

This paper describes the synthesis and characterization of self-assembled organic-inorganic layered perovskite compounds, (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ (n=1-4). the effect of the number of carbon atoms of the alkyl chain length (n) on optical properties has been studied. (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ films fabricated by spin-coating are microcrystalline form, single phase and oriented with the c-axis. Crystallinity, the maximum PL intensity and the lifetime of exciton emissions varied with the number of carbon atoms. the lowest-energy exciton splits into a few fine-structure levels at low temperatures. Time-resolved photoluminescence spectra reveal that (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ shows both singlet and triplet excitons. with decreasing temperature, triplet exciton emissions become dominant for (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ (n=1-3), while (C₆H₅-C₄H₈-NH₃)₂PbBr₄ shows mainly singlet exciton emissions. The intersystem crossing from excited singlet state to triplet state plays an important role in the relaxation process of excitons.     

High pressure behaviour of KHSO4 studied by electrical impedance spectroscopy

Measurements of the electrical conductivity were performed in KHSO₄ at pressures between 0.5 and 2.5 GPa and in the temperature range 120-350 °C by the use of the impedance spectroscopy. The temperatures of the α-β phase transition (T_Tr) and of the melting (T_m), determined from the Arrhenius plots ln(σT) vs. 1/T, increase with pressure up to 1.5 GPa having dT/dP∼+45 K/GPa. Above the pressure 1.5 GPa, the pressure dependencies of T_Tr and T_m are negative dT/dP∼−45 K/GPa. At pressures above 0.5 GPa, the reversible decomposition of KHSO₄ into K₃H(SO₄)₂+H₂SO₄ (and probably into K₅H₃(SO₄)₄+H₂SO₄) affects the electrical conductivity of KHSO₄, with the typical values of the protonic electrical conductivity, c. 10⁻¹ S/cm at 2.5 GPa.     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

Effect of magnetic field in the microhardness studies on calcium hydrogen phosphate crystals

Calcium hydrogen phosphate dihydrate (CaHPO₄·2H₂O, brushite) crystals are grown in gel medium at physiological pH by single diffusion method in the presence of different magnetic field strengths, namely 0, 0.1 and 0.2 Tesla. The results indicate that in the presence of magnetic field, the number of brushite crystals formed at the gel-solution interface reduces and the average size of the crystals increases. This shows that the growth of brushite crystal was favored by magnetism. Vickers and Knoop microhardness studies were carried out on the crystals grown at various magnetic fields. The Vickers (H_V) and Knoop (H_K) microhardness numbers were found to increase with increasing load. The values of Meyer’s index number (n) decrease while the magnetic field strength increases. Nevertheless the n values are greater than 1.6, which shows that the brushite crystals grown under magnetic fields still fall in the soft material category. The brittle index (Bi), yield strength (σ_y) and elastic stiffness constant (c₁₁) were calculated. The Young’s Modulus was calculated using the Knoop hardness value and found to decrease in higher magnetic field strengths.     

Evaluation of desorption activation energy of SiCl2 molecules

The chemical etching of silicon in Cl₂ ambient was considered. The desorption activation energy for an SiCl₂ molecule was evaluated using an experimentally measured dependence of etching rate on concentration of Cl₂ molecules. It was found that the desorption activation energy of SiCl₂ molecules is equal to E_d=(1.605±0.010) eV. This corresponds to a value of the mean lifetime of adsorbed molecules on the surface of τ=46 ms at temperature T=724 K.     

In situ correction of windows’ linear birefringence in ellipsometry measurements

Exact method for in situ correction of windows’ linear birefringence in ellipsometry measurements with an isotropic sample is presented. The method is based on the idea that an unpolarized light is unaffected by a retarding optical element. An optical system was built, in order to simulate an ellipsometry measurement cell with windows with large retardation. The system consisted of two configurations, an “ideal” configuration in which optical retarders were used as windows, and a real life configuration in which sapphire slabs were used as windows. For the measurements with sapphire windows, the ellipsometric parameters of the gold mirror and the nickel foil without the correction yields (ψ,Δ)_Au=(0.66(±0.005),1.56(±0.05)),(ψ,Δ)_Ni=(-0.713(±0.005),1.4(±0.05)). While after the correction the parameters yields (ψ,Δ)_Au=(0.704(±0.006),2.15(±0.1)),(ψ,Δ)_Ni=(0.619(±0.005),2.33(±0.05)), which are in good agreement with our calibration measurements: (ψ,Δ)_Au=(0.709(±0.005),1.98(±0.06)) and (ψ,Δ)_Ni=(0.615(±0.005),2.32(±0.05)).     

Structure and dehydration of the pyrochlore system NaW2−yMoyO6+δ·nH2−zO between 10 and 675 K

The temperature dependence of the structure of the pyrochlore NaW_2−yMo_yO_6+δ·nH_2−zO has been investigated using a variety of diffraction and spectroscopic methods. The positions of OH⁻/H₂O molecules in the structure have been determined. Increases in temperature induce small lattice parameter changes, which are thought to result from movement of the H₂O molecules in the pyrochlore lattice.     

Structure and phase transitions in chloroantimonate(V) crystals: [(C2H5)3NH]SbCl6 and [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl

New triethylammonium salts: [(C₂H₅)₃NH]SbCl₆ (TCA) and [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl (TCAT) have been synthesized. The compounds crystallise in monoclinic symmetry: space groups P2₁/n and P2₁/c, for TCA at 293 K and TCAT at 100 K, respectively. The crystal structure of [(C₂H₅)₃NH]SbCl₆ consists of discrete ionic pairs—triethylammonium cations and hexachloroantimonate anions—linked via the bifurcated N-H?Cl hydrogen bonds. The crystal structure of [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl is composed of three symmetrically independent triethylammonium cations, chlorine anion and two symmetrically independent hexachloroantimonate anions. TCA undergoes a structural phase transition at 336 K (on heating) into the orthorhombic C222 space group, whereas TCAT reveals a structural phase transition at 332 K. The phase transitions are of the first order type. TCA shows a ferroelastic domain structure below 336 K. Differential scanning calorimetry, dilatometric, dielectric dispersion and Raman scattering measurements have been used to study the phase transition mechanisms in these triethylammonium salts.     

Synthesis and characterization of a new monophosphate [2,5-(CH3)2C6H3NH3]H2PO4

Chemical preparation, calorimetric studies, crystal structure and spectroscopic investigations are given for a new noncentrosymmetric organic cation monophosphate [2,5-(CH₃)₂C₆H₃NH₃]H₂PO₄. This compound is orthorhombic P2₁2₁2₁ with the following unit-cell parameters: a=5.872(4), b=20.984(3), c=8.465(1) Å, Z=4, V=1043.0(5) Å³ and D_x=1.396 g cm⁻³. Crystal structure has been solved and refined to R=0.048 using 2526 independent reflections. Structure can be described as an inorganic layer parallel to (a,b) planes between which organic groups [2,5-(CH₃)₂C₆H₃NH₃]⁺ are located. Multiple hydrogen bonds connecting the different entities of compound thrust upon three-dimensional network a noncentrosymmetric configuration.     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

Correlation of fluctuation field and temperature coefficient of coercivity in a CoCrPtB thin film

The effect of the ratio of fluctuation field (H_f) to coercivity (H_c) on the temperature coefficient of coercivity [α(H_c)] was investigated for Co₅₅Cr_15.5Pt₂₈B_1.5/Co₆₃Cr₃₇/Cr, Co₆₉Cr₁₉Pt₉Ta₃/Cr, and Co₈₆Cr₁₀Ta₄/Cr thin films (longitudinal recording media) with very small average grain volume (V_phy). α(H_c) increases markedly with increase in temperature between near 250 and 350 K for Co₅₅Cr_15.5Pt₂₈B_1.5/Co₆₃Cr₃₇/Cr thin films. α(H_c) is approximately proportional to the ratio H_f/H_c for all thin films, as in the case of advanced data backup tapes prepared from ultrafine particles. α(H_c) and the ratio H_f/H_c increase as V_phy decreases. Smaller H_f/H_c values are necessary for small α(H_c) values, which is very important for the thermal stability of high-density recording media with very small V_phy.