Field-induced transition on a triangular plane in the spin-ice compound Dy2Ti2O7

The origin of the lowest-temperature anomaly reported several years ago using a polycrystalline sample of the spin-ice compound Dy2Ti2O7 has remained unresolved. Here we finally clarify its origin by susceptibility measurements down to 65 mK using single crystals under accurate control of the magnetic fields in two independent directions. We demonstrate that the transition is induced under a subtle field combination that precisely cancels the nearest-neighbor spin interactions acting on the spins on the triangular lattice within the pyrochlore structure. Contrary to the other two field-induced transitions, this transition is driven only by the interactions beyond the nearest neighbors. Our observation thus provides the first qualitative evidence for the essential importance of the dipolar interaction beyond the nearest neighbors in the spin ice.     

Quadrupole interactions and relaxation effects in Dy2Ti2O7

Studies of quadrupole interactions and relaxation phenomena in Dy₂Ti₂O₇ at various temperatures up to 750 K have been performed using the Mössbauer effect of the 25.6 keV transition in ¹⁶¹Dy. The source used was ¹⁶¹Tb in ¹⁶⁰Gd₂Ti₂O₇ at 150 K, which emits a very narrow 25.6 keV γ line. Quadrupole interaction parameters and relaxation times, as function of temperature, were deduced from the measurements.     

Temperature‐dependent Raman scattering studies of the geometrically frustrated pyrochlores Dy2Ti2O7, Gd2Ti2O7 and Er2Ti2O7

The temperature‐dependent Raman studies of A₂Ti₂O₇(A = Dy, Er, Gd) were performed on single crystals and polycrystalline samples in the 4.2–295 K temperature range. The Raman spectra showed softening of the majority of phonon modes upon cooling in the whole temperature range studied and large decrease of linewidths. These changes have been analyzed in terms of strong third‐order phonon–phonon anharmonic interactions. Moreover, the 312 and 330 cm⁻¹ modes of Er₂Ti₂O₇(Gd₂Ti₂O₇) showed hardening upon cooling down to about 130 K (100 K) and then anomalous softening below this temperature. The observed anomalous behavior of the Raman modes indicates that some important changes occur in these materials at low temperatures. However, the origin of this behavior is still not clear. Copyright © 2008 John Wiley & Sons, Ltd.     

Quantum-classical reentrant relaxation crossover in Dy2Ti2O7 spin ice

We have studied spin relaxation in the spin ice compound Dy2Ti2O7 through measurements of the ac magnetic susceptibility. While the characteristic spin-relaxation time (tau) is thermally activated at high temperatures, it becomes almost temperature independent below T(cross) approximately 13 K. This behavior, combined with nonmonotonic magnetic field dependence of tau, indicates that quantum tunneling dominates the relaxational process below that temperature. As the low-entropy spin ice state develops below T(ice) approximately 4 K, tau increases sharply with decreasing temperature, suggesting the emergence of a collective degree of freedom for which thermal relaxation processes again become important as the spins become strongly correlated.     

Magnetic ordering in the spin-ice candidate Ho2Ru2O7

Neutron scattering measurements on the spin-ice candidate material Ho2Ru2O7 have revealed two magnetic transitions at T approximately 95 and approximately 1.4 K to long-range ordered states involving the Ru and Ho sublattices, respectively. Between these transitions, the Ho3+ moments form short-ranged ordered spin clusters. The internal field provided by the ordered S=1 Ru4+ moments disrupts the fragile spin-ice state and drives the Ho3+ moments to order. We have directly measured a slight shift in the Ho3+ crystal field levels at 95 K from the Ru ordering.     

Specific heat of Dy2Ti2O7 in magnetic fields: comparison between single-crystalline and polycrystalline data

We report the specific heat of single crystals of the spin ice compound Dy₂Ti₂O₇ under magnetic fields down to 1.8 K. Our polycrystalline results down to 0.4 K are fully consistent with the previous report by Ramirez et al. For the magnetic field along the [100] direction, C_spin/T is interpreted as one Schottky peak characterized by the Zeemann splitting of the Ising levels of all four equivalent spins for each tetrahedron. However, for the magnetic field along the [111] direction, C_spin/T is interpreted as two-component Schottky peak reflecting the fact that there are two kinds of spin components. Along the [110] direction, it is also interpreted as two-component Schottky peak because of experimental misalignment. We found that the features of the polycrystalline data in magnetic fields cannot be reconstructed by simply taking appropriate averages of the present anisotropic single-crystalline data.     

强耦合磁失措自旋冰系统Dy2Ti2O7单晶生长和基本磁性质测量

利用红外光源浮区法生长出大尺寸、高质量的磁失措自旋冰化合物Dy2Ti2O7单晶体.X射线衍射实验证实晶体具有面心立方结构,空间群为 Fd3m,晶胞参数a＝1.0112(2) nm,[111]和[400]方向X射线衍射摇摆曲线半高宽分别仅为0.07°和0.05°.直流磁化率与温度关系测量给出晶体的Van Vleck顺磁因子为2.46×10-5 m3/mol,有效磁矩μeff＝10.24(4)μB,Cure-Weiss温度ΘCW＝1.1 K,揭示Dy2Ti2O7具有弱的铁磁性.对磁性起源的综合分析表明,该自旋冰晶体磁性质主要来源于磁偶极相互作用,且相关最近邻长程偶极相互作用能量标度Dnn＝3.00 K.     

Dy2Ti2O7 spin ice: a test case for emergent clusters in a frustrated magnet

Dy2Ti2O7 is a geometrically frustrated magnetic material with a strongly correlated spin ice regime that extends from 1 K down to as low as 60 mK. The diffuse elastic neutron scattering intensities in the spin ice regime can be remarkably well described by a phenomenological model of weakly interacting hexagonal spin clusters, as invoked in other geometrically frustrated magnets. We present a highly refined microscopic theory of Dy2Ti2O7 that includes long-range dipolar and exchange interactions to third nearest neighbors and which demonstrates that the clusters are purely fictitious in this material. The seeming emergence of composite spin clusters and their associated scattering pattern is instead an indicator of fine-tuning of ancillary correlations within a strongly correlated state.     

Local Disorder in Ln2Ti2O7 (Ln = Gd,Tb, Dy) Pyrochlores

JETP Letters - The orientational dynamics in the isotropic phase of a comb-like nematic polymer with mesogenic and functional side groups is studied using the Kerr effect and dielectric...     

Observation of a liquid-gas-type transition in the pyrochlore spin ice compound Dy2Ti2O7 in a magnetic field

Low temperature magnetization measurements on the pyrochlore spin ice compound Dy2Ti2O7 reveal that the ice-rule breaking spin flip, appearing at H approximately 0.9 T applied parallel to the [111] direction, turns into a novel first-order transition for T<0.36 K which is most probably of a liquid-gas type. T-linear variation of the critical field observed down to 0.03 K suggests the unusual situation that the entropy release across the transition remains finite [approximately 0.5 (J/K) x mol-Dy] as T-->0, in accordance with a breaking of the macroscopic degeneracy in the intermediate "kagomé ice" state.     

Experimental observations of ferroelectricity in double pyrochlore Dy2Ru2O7

Double pyrochlore Dy2Ru207 is synthesized and its magnetism and ferroelectricity below the Ru4＋ spin ordering temperature （NI00 K） are investigated. The ferroelectric transition appears at -18 K, much higher than the Dy3＋ spin ordering point at -1.8 K and lower than the Ru4＋ spin ordering point at -100 K. The measured electric polarization at ,-2 K is as big as 145℃/m2 in the polycrystalline samples. It is argued that the ferroelectricity is possibly ascribed to the electric dipole ordering arising from the collective monopole excitations in the Dy3＋ tetrahedrons in prior to the Dy3＋ spin ordering into spin-ice like state below -1.8 K.     

Crystal field and magnetoelastic interactions in Tb2Ti2O7

In terms of a semiphenomenological exchange charge model, we have obtained estimates of parameters of the crystal field and parameters of the electron-deformation interaction in terbium titanate Tb₂Ti₂O₇ with a pyrochlore structure. The obtained set of parameters has been refined based on the analysis of spectra of neutron inelastic scattering and Raman light scattering, field dependences of the forced magnetostriction, and temperature dependences of elastic constants.     

Ferrimagnetic properties of Eu3Ti2O7

The Mossbauer spectrum of ¹⁵¹Eu₃Ti₂O₇ reveals a ferrimagnetic ordering below (8 ± 0.3) K with two inequivalent sites in ratio 2: 1, and with exchange constants nearly equal to those of EuTiO₃ and of Eu₂TiO₄. The sublattice magnetizations are explained in terms of these constants.     

Phase stability and pressure dependence of defect formation in Gd2Ti2O7 and Gd2Zr2O7 pyrochlores

We report dramatically different behaviors between isostructural Gd2Ti2O7 and Gd2Zr2O7 pyrochlore at pressures up to 44 GPa, in which the substitution of Ti for Zr significantly increases structural stability. Upon release of pressure, the Gd2Ti2O7 becomes amorphous. In contrast, the high-pressure phase of Gd2Zr2O7 transforms to a disordered defect-fluorite structure. First-principle calculations for both compositions revealed that the response of pyrochlore to high pressure is controlled by the intrinsic energetics of defect formation.     

Diffuse ferroelectric phase transition in Li2Pb2Dy2W2Ti4V4O30

Tungsten–bronze polycrystalline ceramic Li₂Pb₂Dy₂W₂Ti₄V₄O₃₀ was prepared by mixed-oxide method. The preparation conditions were optimized by thermogravimetry analysis and repeated firing. Room-temperature structural analysis confirms the formation of the compound in single phase (orthorhombic). Studies of dielectric parameters () of the compound with temperature at different frequencies suggest the existence of phase transition in the compound. The existence of ferroelectric property (based on dielectric anomaly) of the material was confirmed by polarization study.     

Transitions and Spin Dynamics at Very Low Temperature in the Pyrochlores Yb2Ti2O7 and Gd2Sn2O7

An orientational disorder of the cation in [(PyO)D][AuCl₄] crystal was investigated by the ³⁵Cl NQR and ¹H NMR measurements. A structural phase transition was found at ca. 70 K from the temperature dependence of the NQR frequencies both in [(PyO)D][AuCl₄] and [(PyO)H][AuCl₄]. Temperature dependence of the spin-lattice relaxation time T ₁ of the NQR of [AuCl₄]⁻ could be interpreted by an electric field gradient modulation due to the motion of the cation. Characteristics of T ₁ of ³⁵Cl NQR as well as that of ¹H NMR suggest a dynamic orientational disorder of the cation.     

Ion-exchange between Na2Ti3O7 and H2Ti3O7 nanosheets at different pH levels: An experimental and first-principles study

The models of Na_2−xH_xTi₃O₇ (x=0, 1, and 2) nanosheets were proposed to investigate the formation energies of ion-exchange using first-principles calculations. The calculated results demonstrated that sodium titanate nanosheet is energetically favorable for ion-exchange in a wide pH range, from acidic solution to even highly concentrated alkaline aqueous solution due to the negative formation energies. Therefore, the composition of sodium titanate nanosheet in alkaline solution should be Na_2−xH_xTi₃O₇ (0<x≤2) rather than Na₂Ti₃O₇. The formation energies of ion-exchange decrease with the pH decreasing. As a result, the thermodynamic driving force of ion-exchange is enhanced at low pH level. To further verify the calculated results, the ion-exchange properties of a series of titanate nanosheets in aqueous solutions at different pH levels were investigated. The experimental results are in good agreement with the theoretical deduction.