Magnetic structure of a RbDy(WO4)2 single crystal

The results of measuring the temperature and field dependences of the magnetization of a RbDy(WO₄)₂ single crystal in the temperature range from 4.2 to 50 K and in magnetic fields up to 1.6 T are presented. The energies of the exchange and dipole-dipole interactions are estimated. The magnetic structure of the ground state is determined. Fiz. Tverd. Tela (St. Petersburg) 41, 672–676 (April 1999)     

The effect of hydration on the photo-deactivation pathways of 4-aminopyrimidine

The influence of water on the photo-deactivation process of 4-aminopyrimidine has been investigated by means of microsolvation and continuum solvation models. Two- and four-water models were used for the former purpose. Vertical excitations, stationary points on the first excited singlet surface, conical intersections (minima on the crossing seam) and reaction paths have been investigated at the state-averaged complete active space self-consistent field (CASSCF) and multistate CAS perturbation theory to second order (MS-CASPT2) levels of theory. A destabilizing effect of 0.2–0.3 eV has been observed for nπ∗ states while the ππ∗ state is almost unaffected. The two-water model gives already a good representation of hydration effects, especially when combined with the continuum model. A small enhancement of energy barriers (∼0.1 eV) is observed leading to the conclusion that the photodynamics of 4-aminopyrimidine should be affected only little by these solvent effects.     

The phase diagram for coexisting d-wave superconductivity and charge-density waves: cuprates and beyond

Phase diagrams of d-wave superconductivity characterized by an order parameter Δ coexisting with charge-density waves (CDWs) characterized by an order parameter Σ were constructed for the two-dimensional Fermi surface (FS) appropriate to, e.g., cuprates. CDWs were considered as an origin of the pseudogap appearing at antinodal FS sections of the d(x2-y2) superconductor. Two types of the Σ-reentrance were found: with the temperature, T, and with the opening of the CDW sector, 2α. The angular plots in the momentum space for the resulting gap profile over the FS ('gap roses') were obtained. The gap patterns are rather involved, giving insight into the difficulties of the interpretation of photoemission spectra. It was shown that the Σ-Δ coexistence region exists even for the complete dielectric gapping due to the distinction between the superconducting and CDW order parameter symmetries. The checkerboard and unidirectional CDW configurations were examined, and both the phase diagrams and the behavior with T and α of the order parameters were found to differ. A more general case with a non-zero mismatch angle β between the superconducting lobes and the CDW sectors was analyzed, the case β = π/4 corresponding to the d(xy) symmetry of the superconducting order parameter. The phase diagrams were found to be sensitive to β-variations, showing that internal strains and external pressure can drastically affect the behavior of Σ(T) and Δ(T).     

Enhancement of local superconductivity in ferromagnetic FeCrB metallic glass by Ar+ ion irradiation

We have reinforced local superconductivity in ferromagnetic Fe(67)Cr(18)B(15) metallic glasses by ion irradiation. Superconductivity in this medium appears due to the presence of large-scale layered clusters of metallic Fe-Cr phase, 150-230 ? in size, with a ferromagnetic (or superparamagnetic) Fe-rich core and nonmagnetic Cr-rich superconducting shell. Here we show that due to the intensification of concentration phase separation in the Fe-Cr clusters under ion (Ar(+)) irradiation, the volume of the superconducting phase increases from the initial 0.4-0.5% up to 7-8%. After irradiation, the resistivity jump Δρ/ρ in the temperature range T=3.1-3.6 K increases ～14 times, reaching 19%, as compared to 1.36% for the initial sample. In the interval of T=3.1-3.6 K, the rate of resistance change reaches 79% K(-1) for the irradiated sample instead of 3.6% K(-1) for the initial sample. In the same temperature interval, the rate of magnetoresistance change increases from 3% K(-1) for the initial sample up to 70% K(-1) after irradiation.     

Temperature and pressure dependences of EPR spectra of Gd ion doped in the EuAl3(BO3)4 monocrystal

The ground state of Gd³⁺ ions substituting for trivalent europium in the EuAl₃(BO₃)₄ single crystal was studied by electron paramagnetic resonance (EPR) over the temperature range of 300-4.2 K and at pressures up to 9 kbar. The EPR spectra were analysed using the spin Hamiltonian of axial symmetry. The following parameters are reported: g=1.981±0.002, b₂⁰=280.18±0.12, b₄⁰=−12.95±0.08 and b₆⁰=0.61±0.12 (at Т=298 K). The distortions of the nearest environment of Gd³⁺ ion were analysed within the framework of the superposition model of crystal field.     

Investigation of magnetic phase transformations in a system of Nd1−x BaxMnO3−δ (0≤x≤0.50) depending on the conditions of preparation

Investigations are performed of the crystal structure and magnetic and electromagnetic properties of single crystals (0.23 ≤x≤0.34) and polycrystals (0 ≤x ≤0.50) of an Nd_1?x Ba_xMnO_3?δ system of solid solutions. It is found that, for samples prepared in the air, the maximal Curie temperature (T _C ) does not exceed 150 K, while, in the case of polycrystalline samples in the concentration range of 0.34 ≤x ≤0.50, prepared in a reducing medium (a gaseous mixture of argon and carbon monoxide), T _C increases to 320 K. As a result of the reducing medium effect on the compositions, the type of the magnetic phase transition to the paramagnetic state changes from the first to second order. The electrical resistivity of reduced polycrystalline samples (0.34≤x ≤0.50) decreases in magnitude and correlates with the behavior of magnetization. Both series of samples, prepared both in the air and in a reducing medium, exhibit a transition from the metal to dielectric state at a temperature below T _C . The temperature and field dependences of magnetization for the stoichiometric polycrystalline com-position of Nd_0.50Ba_0.50MnO₃ are measured under conditions of hydrostatic pressure. It is demonstrated that the hydrostatic pressure induces in Nd_0.50Ba_0.50MnO₃ the transition from the antiferromagnetic to ferromagnetic state. Based on the measurement results, hypothetical magnetic phase diagrams are constructed for the system of solid solutions being treated, depending on the concentration of barium and the method of preparation. It is found that no T _TC increase is observed in single crystals (0.23≤x≤0.34) such as is observed in polycrystals. It is assumed that the abrupt increase in T _C of polycrystalline samples prepared in a reducing medium is a result of the emergence of extended defects and microstresses in the crystal lattice.     

Magnetostriction studies of magnetic phase transitions in the copper metaborate CuB2O4

The field dependences of the longitudinal and transversal magnetostriction of the copper metaborate CuB₂O₄ were measured at various temperatures below the Néel point in magnetic fields directed along the tetragonal axis or in the basal plane. Magnetostriction was found to exhibit jumps at magnetic-field-induced phase transitions to a commensurate weak ferromagnetic state, as well as to grow smoothly in fields above and below the critical level. The magnetostriction observed in a magnetic field directed along the tetragonal axis is shown to be primarily caused by volume dilatation of the crystal. The experimental data obtained were used to construct the magnetic phase diagram of copper metaborate magnetized along the tetragonal axis.     

Structure and physical properties of layered double perovskite NdBaCo2O5.50 + δ (δ ≈ 0.25)

Magnetic, electric, and elastic properties of the crystal and magnetic structure of double layered perovskite NdBaCo₂O_{5.50 + δ} are studied by the neutron diffraction method at various temperatures. The data are analyzed using two models of crystal structure. In the first model, the sample consists of two crystal-structure phases with ordered and disordered arrangements of oxygen vacancies. In the second model, a new crystal-structure phase is formed in this compound, which is characterized by ordering of oxygen vacancies in the plane of the rare-earth ion in the 1c crystallographic position (0, 0, 1/2) of space group Pmmm. Two crystal-structure models correspond to different types of magnetic ordering (a mixture of a ferromagnetic phase and a G-type antiferromagnetic phase is presumed in the two-phase crystal-structure model, while a canted antiferromagnetic structure is presumed in the one-phase crystal structure model). The behavior of electric and elastic parameters is better described in the first model, while neutron diffraction studies are in better agreement with the second model.     

Photodynamical simulations of cytosine: characterization of the ultrafast bi-exponential UV deactivation

Deactivation of UV-excited cytosine is investigated by non-adiabatic dynamics simulations, optimization of conical intersections, and determination of reaction paths. Quantum chemical calculations are performed up to the MR-CISD level. Dynamics simulations were performed at multiconfigurational level with the surface hopping method including four electronic states. The results show the activation of four distinct reaction pathways at two different subpicosecond time scales and involving three different conical intersections. Most trajectories relax to a minimum of the S(1) state and deactivate with a time constant of 0.69 ps mainly through a semi-planar conical intersection along the n(O)π* surface. A minor fraction deactivate along ππ* regions of the S(1) surface. Sixteen percent of trajectories do not relax to the minimum and deactivate with a time constant of only 13 fs.     

Influence of cation substitution on the magnetic properties of the FeCr2S4 ferrimagnet

The influence of cation substitution on the magnetic properties of single and polycrystals of FeCr₂S₄ spinel has been studied. The tetrahedral A-site substitution of the Fe by Cu in Fe_1−xCu_xCr₂S₄ was found to increase significantly the value of temperature T_m of the spin-glass like magnetization anomaly, whereas the octahedral B-site substitution of the Cr by In decreases T_m. This effect is suggested to result from a structural transformation influenced by variation of internal (chemical) pressure due to lattice contraction (Cu) or expansion (In). The observed reduced values of the Curie temperature for Cu-substituted single crystals compared to that of the polycrystalline samples are attributed to presence of Cl ions in samples detected by electron-probe microanalysis. The observed reduced value of saturation magnetization in the polycrystals compared to the single crystals is ascribed to the effect of surface anisotropy. Based on the experimental data the superexchange is concluded to be the dominant exchange interaction for 0≤x≤0.5 in Fe_1−xCu_xCr₂S₄, whereas the indirect exchange through the charge carriers is considered of minor importance.