We report the crystal growth, crystal structure and basic magnetic properties of a new cobalt-based pyrochlore, NaSrCo$_2$F$_7$. Na and Sr are completely disordered on the non-magnetic large atom A sites, while magnetic S=3/2 Co$^{2+}$ fully occupies the pyrochlore lattice B sites. This system exhibits an isotropic magnetic susceptibility with strong antiferromagnetic interactions ($θ_{CW}$ = -127(1)), a large effective moment (${ρ_{eff}}$ = 5.9(1) ${μ_B}$/Co) and no spin freezing until 3 K. Thus NaSrCo$_2$F$_7$ is a geometrically frustrated antiferromagnet with a frustration index f = -${θ_{CW}}$/T$_f$ = 42. AC susceptibility, DC susceptibility, and heat capacity are utilized to characterize the spin freezing at low temperatures. We propose that NaSrCo$_2$F$_7$, compared here to the related material NaCaCo$_2$F$_7$, may be the realization of a frustrated pyrochlore antiferromagnet with weak bond disorder. The strong magnetic frustration at an easily accessible temperature and the availability of large single crystals make this one of the potentially interesting alternatives to the more commonly studied rare earth oxide pyrochlores.
A new charge-ordered magnetically frustrated mixed-metal fluoride with a pyrochlore-related structure has been synthesized and characterized. The material, RbFe2F6 (RbFe2+Fe3+F6) was synthesized through mild hydrothermal conditions. The material exhibits a three-dimensional pyrochlore-related structure consisting of corner-shared Fe2+F6 and Fe3+F6 octahedra. In addition to single crystal diffraction data, neutron powder diffraction and magnetometry measurements were carried out. Magnetic data clearly reveal strong antiferromagnetic interactions (a Curie-Weiss temperature of -270 K) but suffici…
We present time-of-flight neutron total scattering and polarized neutron scattering measurements of the magnetically frustrated compounds NaCaCo$_2$F$_7$ and NaSrCo$_2$F$_7$, which belong to a class of recently discovered pyrochlore compounds based on transition metals and fluorine. The magnetic pair distribution function (mPDF) technique is used to analyze and model the total scattering data in real space. We find that a previously-proposed model of short-range XY-like correlations with a length scale of 10-15 Å, combined with nearest-neighbor collinear antiferromagnetic correlations, accurat…
NaCaNi$_2$F$_7$ is an insulating, frustrated A$_2$B$_2$F$_7$ pyrochlore with magnetic S = 1 Ni$^{2+}$ on the pyrochlore B site. Non-magnetic Na and Ca are disordered on the A-site. Magnetic susceptibility measurements made on an oriented single crystal, grown in a floating zone furnace, show isotropic behavior at temperatures between 5 and 300 K, with an effective moment of 3.7 $μ_B$/Ni. Despite displaying a large Curie-Weiss theta (-129 K), spin-ordering-related features are not seen in the susceptibility or specific heat until a spin glass transition at 3.6 K. This yields an empirical frustr…
Inelastic neutron scattering measurement is performed on a breathing pyrochlore antiferromagnet Ba3Yb2Zn5O11. The observed dispersionless excitations are explained by a crystalline electric field (CEF) Hamiltonian of Kramers ion Yb3+ of which the local symmetry exhibits C3v point group symmetry. The magnetic susceptibility previously reported is consistently reproduced by the energy scheme of the CEF excitations. The obtained wave functions of the ground state Kramers doublet exhibit the planer-type anisotropy. The result demonstrates that Ba3Yb2Zn5O11 is an experimental realization of breathi…
We investigate the connection between highly frustrated kagome based Hamiltonians and a recently synthesized family of materials containing Ti3+ S=1/2 ions. Employing a combination of all electron density functional theory and numerical diagonalization techniques, we establish the Heisenberg Hamiltonians for the distorted kagome antiferromagnets Rb2NaTi3F12, Cs2NaTi3F12 and Cs2KTi3F12. We determine magnetization curves in excellent agreement with experimental observations. Our calculations successfully clarify the relationship between the experimental observations and the magnetization-plateau…
Realization of the Ruby Lattice Antiferromagnet in Layered Transition-Metal Fluorides
Research Institute for Interdisciplinary Science, Okayama University（冈山大学跨学科科学研究所）；Technische Hochschule Brandenburg（勃兰登堡理工大学）；Institute of Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院物理研究所）
In perovskite-type compounds, the interplay of cooperative Jahn-Teller effect, electronic correlations and orbital degree of freedom leads to intriguing properties. $\mathrm{NaCrF_{3}}$ is a newly synthesized Jahn-Teller active fluoroperovskite where the $\mathrm{CrF_{6}^{4-}}$ octahedrons are considerably distorted. Based on the first-principles calculation, we analyze its electronic structure and magnetic properties. Our numerical results show that the $\mathrm{Cr^{2+}}$ ions adopt the high-spin $t_{2g\uparrow}^{3}e_{g\uparrow}^{1}$ configuration with $G$-type orbital ordering. We also estim…
We report the systematic study of structural, magnetic and electrical transport properties of $Y_{2-x}Bi_xIr_2O_7$ (x = 0.0, 0.1, 0.2, 0.3) pyrochlore iridates. The chemical doping enhances electrical conductivity and antiferromagnetic correlation substantially. The replacement of non-magnetic $Y^{3+}$ ion with non-magnetic $Bi^{3+}$ in $Y_2Ir_2O_7$ tends to reduce the octahedral distortion thus enhancing the antiferromagnetic correlation. Raman spectroscopy shows that the $Ir-O$ bond contract slightly and the $R-O'$ bond turn longer as disorder and phononic oscillation are reduced with $Bi$ d…
Most works on pyrochlore magnets deal with the interacting spin-1/2 local moments. We here study the spin-one local moments on the pyrochlore lattice, and propose a generic interacting spin model on a pyrochlore lattice. Our spin model includes the antiferromagnetic Heisenberg interaction, the Dzyaloshinskii-Moriya interaction and the single-ion spin anisotropy. We develop a flavor wave theory and combine with a mean-field approach to study the global phase diagram of this model and establish the relation between different phases in the phase diagram. We find the regime of the quantum paramagn…
We report the magnetic characterization of the frustrated transition metal pyrochlore NaCaCo$_2$F$_7$. This material has high spin Co$^{2+}$ in CoF$_6$ octahedra in a pyrochlore lattice, and disordered non-magnetic Na and Ca on the large-atom sites in the structure. Large crystals grown by the floating zone method were studied. The magnetic susceptibility is isotropic, the Co moment is larger than the spin-only value, and in spite of the large Curie Weiss theta (-140 K), freezing of the spin system, as characterized by peaks in the ac and dc susceptibility and specific heat, does not occur unt…
The spinel oxides LiGaCr4O8 and LiInCr4O8 contain size-alternating pyrochlore lattices of spin-3/2 Cr3+ tetrahedra with different magnitudes of alternation. We show here that the solid solutions LiGa1-xInxCr4O8 between these two 'breathing' pyrochlore compounds display (i) rapid suppression of magnetic and structural transitions upon doping the end members, (ii) spin-glass-like freezing above 2 K in the range 0.1 $\lesssim$ x $\lesssim$ 0.6, and (iii) apparent spin-gap behavior for x $\gtrsim$ 0.7. Furthermore, no transitions are observed above 2 K at x ~ 0.9, where magnetic susceptibility rem…
Based on geometry optimization and magnetic structure investigations within density functional theory, unique uranium nitride fluoride UNF, isoelectronic with UO2, is shown to present peculiar differentiated physical properties. Such specificities versus the oxide are related with the mixed anionic sublattices and the layered-like tetragonal structure characterized by covalent like [U2N2]2+motifs interlayered by ionic like [F2]2- ones and illustrated herein with electron localization function graphs. Particularly the ionocovalent chemical picture shows, based on overlap population analyses, st…
We report a comprehensive study on the magnetic and structural properties of the spinel sulfides LiInCr4S8, LiGaCr4S8, and CuInCr4S8, where Li+/Cu+ and Ga3+/In3+ ions form a zinc-blende-type order. On the basis of synchrotron X-ray diffraction and magnetization data obtained using polycrystalline samples, these three sulfides are suggested to be breathing pyrochlore magnets with alternating antiferromagnetic and ferromagnetic interactions on the small and large tetrahedra, respectively. The measured magnetization processes of the three sulfides up to 72 T are significantly different. The magne…
Theory of Two-Step Magnetic Ordering Phenomena in a Geometrically Frustrated Heisenberg Pyrochlore Antiferromagnet with Long Range Dipolar Interactions
利用平均场论研究了具有交换作用和偶极-偶极相互作用的烧绿石晶格上的海森堡反铁磁体模型。在处理偶极通过使用埃瓦尔德方法，一个软（临界）模式与一个独特的有序波矢量被选择为所有强度的偶极偶极耦合。对于弱偶极子，选择部分有序的三个子晶格自旋结构（P态），其中q_{ord} =（1/2 1/2 1/2）。一个完全有序的四个子晶格自旋结构（F态），q =（000），与P态竞争，并随着温度的降低而成为稳定的结构。我们的结果进行了比较，对其他的理论计算和连接到最近的实验结果Gd 2 Ti 2 O 7进行了讨论。
We investigate novel topological magnon band crossings of pyrochlore antiferromagnets with all-in-all-out (AIAO) magnetic order. By general symmetry analysis and spin-wave theory, we show that pyrochlore materials with AIAO orders can host Weyl magnons under external magnetic fields or uniaxial strains. Under a small magnetic field, the magnon bands of the pyrochlore with AIAO background can feature two opposite-charged Weyl points, which is the minimal number of Weyl points realizable in quantum materials and has not be experimentally observed so far. We further show that breathing pyrochlore…
Using $\rm Er_2Ti_2O_7$ as a motivation, we investigate finite-field properties of $XY$ pyrochlore antiferromagnets. In addition to a fluctuation-induced six-fold anisotropy present in zero field, an external magnetic field induces a combination of two-, three-, and six-fold clock terms as a function of its orientation providing for a rich and controllable magnetothermodynamics. For $\rm Er_2Ti_2O_7$, we predict a new phase transition for ${\bf H}\parallel [001]$. Re-entrant transitions are also found for ${\bf H}\parallel [111]$. We extend these results to the whole family the $XY$ pyrochlore…
On the basis of the first-principles evolutionary crystal structure prediction of stable compounds in the Cu-F system, we predict two experimentally unknown stable phases -- Cu2F5 and CuF3. Cu2F5 comprises two interacting magnetic subsystems with the Cu atoms in the oxidation states +2 and +3. CuF3 contains magnetic Cu 3+ ions forming a lattice with the antiferromagnetic coupling. We showed that some or all of Cu 3+ ions can be reduced to Cu 2+ by electron doping, as in the well known KCuF3. Significant similarities between the electronic structures calculated in the framework of DFT+U suggest…
We report neutron scattering measurements of the spinel oxide LiGaCr$_{4}$O$_{8}$, in which magnetic ions Cr$^{3+}$ form a breathing pyrochlore lattice. Our experiments reveal the coexistence of a nearly dispersionless resonance mode and dispersive spin wave excitations in the magnetically ordered state, which can be quantitatively described by a quantum spin model of hexagonal loops and linear spin wave theory with the same set of exchange parameters, respectively. Comparison to other Cr spinel oxides reveals a linear relationship between the resonance energy and lattice constant across all t…
We present synchrotron x-ray diffraction, neutron powder diffraction and time-of-flight inelastic neutron scattering measurements on the rare earth pyrochlore oxide Nd2Zr2O7 to study the ordered state magnetic structure and cystal field states. The structural characterization by high-resolution synchrotron x-ray diffraction confirms that the pyrochlore structure has no detectable O vacancies or Nd/Zr site mixing. The neutron diffraction reveals long range all-in/all-out antiferromagnetic order below T_N ~ 0.4 K with propagation vector k = (0 0 0) and an ordered moment of 1.26(2) μ_B/Nd at 0.1 …
Unified Description of Spin-Lattice Coupling and Thermodynamics in the Pyrochlore Heisenberg Antiferromagnet
Institute for Solid State Physics, The University of Tokyo（东京大学固体物理研究所）；Department of Physics, The University of Tokyo（东京大学物理系）；Department of Chemistry, Graduate School of Science, Kyoto University（京都大学理学研究科化学系）；Research Center for Materials Nanoarchitectonics, National Institute for Materials Science（国立材料科学研究所材料纳米结构研究中心）；Department of Engineering Science, University of Electro-Communications（电气通信大学工学部）
Theory of paramagnetic scattering in highly frustrated magnets with long-range dipole-dipole interactions: The case of the Tb2Ti2O7, pyrochlore antiferromagnet
由稀土磁矩组成的高阻挫反铁磁体是目前实验和理论研究的热点。稀土离子通常具有小的交换相互作用和大的磁矩。这使得有必要详细了解长程磁偶极-偶极相互作用在这些系统中的作用，特别是在顺磁相中发展的自旋-自旋相关性的背景下，但通常无法凝聚成常规的长程磁有序相。这种情况在受抑烧绿石反铁磁体材料Tb 2 Ti 2 O 7中得到最显著的强调，尽管反铁磁居里-外斯温度Tcw ~ -20 K，但Tb 2 Ti 2 O 7在低至50 mK时不有序。在本文中，我们报告的结果从平均场论计算的顺磁弹性中子散射的高度挫折的磁系统与长程偶极-偶极相互作用，重点是Tb 2 Ti 207系统。将Tb_2Ti_2O_7模拟为反铁磁<111>Ising烧绿石，发现平均场顺磁散射与实验观测结果不一致.通过简单的对称性参数，我们表明，所观察到的Tb 2 Ti 207中的顺磁相关被排除由任何自旋哈密顿量，认为只有伊辛自旋，但定性一致的海森堡矩。明确计算的顺磁散射模式的<111>伊辛和海森堡模型，其中包括有限的单离子各向异性，支持这些主张。我们提供的建议，调和需要恢复自旋各向同性与伊辛样结构所建议的单离子性质的Tb 3+。
The ordering of the classical Heisenberg model on the pyrochlore lattice with the antiferromagnetic nearest-neighbor interaction J1 and the ferromagnetic next-nearest-neighbour interaction J2 is investigated by means of a mean-field analysis and a Monte Carlo simulation. For a moderate J2/J1-value, the model exhibits a first-order transition into an incommensurate multiple-q ordered state where multiple Bragg peaks coexist in the spin structure factor. We show that there are two types of metastable multiple-q states, a cubic symmetric sextuple-q state and a non-cubic symmetric quadruple-q stat…
We explore the field-temperature phase diagram of the XY pyrochlore antiferromagnet Er$_2$Ti$_2$O$_7$, by means of magnetization and neutron diffraction experiments. Depending on the field strength and direction relative to the high symmetry cubic directions $[001], [1\bar{1}0]$ and $[111]$, the refined field induced magnetic structures are derived from the zero field $ψ_2$ and $ψ_3$ states of the $Γ_5$ irreducible representation which describes the ground state of XY pyrochlore antiferromagnets. At low field, domain selection effects are systematically at play. In addition, for $[001]$, a pha…
FeF$_3$, with its half-filled Fe$^{3+}$ $3d$ orbital, hence zero orbital angular momentum and $S=5/2$, is often put forward as a prototypical highly-frustrated classical Heisenberg pyrochlore antiferromagnet. By employing {\it ab initio} density functional theory (DFT), we obtain an effective spin Hamiltonian for this material. This Hamiltonian contains nearest-neighbor antiferromagnetic Heisenberg, bi-quadratic and Dzyaloshinskii-Moriya interactions as dominant terms and we use Monte Carlo simulations to investigate the nonzero temperature properties of this minimal model. We find that upon d…
We investigate spin correlations in the dipolar Heisenberg antiferromagnet Gd2Sn2O7 using polarised neutron-scattering measurements in the correlated paramagnetic regime. Using Monte Carlo methods, we show that our data are sensitive to weak further-neighbour exchange interactions of magnitude ~0.5% of the nearest-neighbour interaction, and are compatible with either antiferromagnetic next-nearest neighbour interactions, or ferromagnetic third-neighbour interactions that connect spins across hexagonal loops. Calculations of the magnetic scattering intensity reveal rods of diffuse scattering al…
Rare-earth pyrochlores are known to exhibit exotic magnetic phenomena. We report a study of crystal growth and characterizations of a new rare-earth compound Er$_2$AlSbO$_7$, in which Al$^{3+}$ and Sb$^{5+}$ ions share the same positions with a random distribution. The magnetism are studied by magnetic susceptibility, specific heat and thermal conductivity measurements at low temperatures down to several tens of milli-kelvin. Different from the other reported Er-based pyrochlores exhibiting distinct magnetically ordered states, a spin-freezing transition is detected in Er$_2$AlSbO$_7$ below 0.…
Low temperature specific heat and possible gap to magnetic excitations in the Heisenberg pyrochlore antiferromagnet Gd2Sn207
Gd_2Sn_2O_7烧绿石海森堡反铁磁体在1 K附近出现了向四个亚晶格Neel有序态的相变。尽管有序状态的表面上是传统的性质，但比热在350-800 mK的温度范围内被发现由反常的T平方幂定律描述。另一种烧绿石海森堡材料Gd 2 Ti 2 O 7也有类似的温度依赖性。Cv中这种反常的T平方行为被认为与态密度的不寻常的能量依赖性有关，这种不寻常的能量依赖性似乎也表现在μ子自旋弛豫实验中发现的低温自旋涨落中。在本文中，我们报告的Cv的计算，考虑自旋波一样的激发的Neel秩序中观察到的Gd 2Sn 2 O 7，并认为参数的T平方行为并不反映真正的低能量激发的Gd 2Sn 2 O 7。相反，我们发现这种材料的低能量激发是由单离子和偶极各向异性效应间隙的反铁磁振子，并且在先前的比热测量中考虑的350 mK的最低温度偶然地与交叉温度相一致，低于该交叉温度，磁振子变得热激活，Cv呈指数形式。我们认为，进一步的比热测量，延伸到至少100 mK是必需的，以归因于一个非常规的描述磁激发的基态的Gd 2 Sn 2 O 7或无效的标准图片的间隙激发本文提出的。
We theoretically investigate the low-temperature phase of the recently synthesized Lu$_2$Mo$_2$O$_5$N$_2$ material, an extraordinarily rare realization of a $S=1/2$ three-dimensional pyrochlore Heisenberg antiferromagnet in which Mo$^{5+}$ are the $S=1/2$ magnetic species. Despite a Curie-Weiss temperature ($Θ_{\rm CW}$) of $-121(1)$ K, experiments have found no signature of magnetic ordering $or$ spin freezing down to $T^*\approx0.5$ K. Using density functional theory, we find that the compound is well described by a Heisenberg model with exchange parameters up to third nearest neighbors. The…
The magnetic insulator Gd2Sn2O7 is one of many geometrically frustrated magnetic materials known to exhibit a nonzero muon spin polarization relaxation rate, $λ(T)$, down to the lowest temperature (T) studied. Such behaviour is typically interpreted as a significant level of persisting spin dynamics (PSD) of the host material. In the case of Gd2Sn2O7, such PSD comes as a surprise since magnetic specific heat measurements suggest conventional gapped magnons, which would naively lead to an exponentially vanishing $λ(T)$ as $T \rightarrow 0$. In contrast to most materials that display PSD, the or…
Cobalt pyrochlore fluoride NaCaCo$_2$F$_7$ is a disordered frustrated magnet composed of Co$^{2+}$ ions with an effective spin-$\frac{1}{2}$ magnetic moment and exhibits spin freezing below $T_f \sim$2.4 K. We perform ultrasound velocity measurements on a single crystal of the cubic NaCaCo$_2$F$_7$. The temperature dependence of the bulk modulus (the breathing elastic mode) exhibits Curie-type softening upon cooling below $\sim$20 K down to $T_f$, which is suppressed by the magnetic field. This Curie-type softening should be a precursor to the enhancement of the strength of exchange disorder v…
We present a numerical study of the magnetic structure of nanostructured iron fluoride, using the Monte-Carlo-Metropolis simulated annealing technique and a classical Heisenberg Hamiltonian with a superexchange angle dependence. The parameters are adjusted on experimental results, and the atomic structure and topology taken from a previous atomistic model of grain boundaries in the same system. We find perfect antiferromagnetic crystalline grains and a disordered magnetic configuration (speromagnetic like) at the grain boundary, in agreement with experimental findings. Both the lowest magnetic…
