Crystal Ground State Research Articles

Rare-Earth Chalcogenides: An Inspiring Playground For Exploring Frustrated Magnetism

Abstract The rare-earth chalcogenide $ARECh_{2}$ family ($A =$ alkali metal or monovalent ions, $RE =$ rare earth, $Ch =$ chalcogen) has emerged as a paradigmatic platform for studying frustrated magnetism on a triangular lattice. The family members exhibit a variety of ground states, from quantum spin liquid to exotic ordered phases, providing fascinating insight into quantum magnetism. Their simple crystal structure and chemical tunability enable systematic exploration of competing interactions in quantum magnets. Recent neutron scattering and thermodynamic studies have revealed rich phase diagrams and unusual excitations, refining theoretical models of frustrated systems. This review provides a succinct introduction to $ARECh_{2}$ research. It summarizes key findings on crystal structures, single-ion physics, magnetic Hamiltonians, ground states, and low-energy excitations. By highlighting current developments and open questions, we aim to catalyze further exploration and deeper physical understanding on this frontier of quantum magnetism.

Reconfigurable directional selective tunneling of p-type phonons in polarized elastic wave systems

There have been many studies on the ground state of phononic crystals, but few studies on the nature of the excited state. In this paper, we introduce the asymmetric Klein tunneling method in phononic systems, which enables selective direction and control of elastic waves by inducing polarization through an external field in an artificial barrier. Using tight-binding theory, we systematically studied phononics in a super-honeycomb structure, demonstrating the anisotropic transition properties of excited state phonons through a matrix model involving the ground state’s s-type and the first excited state’s p-type wave functions. Additionally, we exploit the thermal sensitivity of epoxy to achieve localized thermal field-induced distortion of the bottom flat band, forming a tiled Dirac cone, and thereby creating a reconfigurable polarized artificial barrier in the elastic wave system. Elastic waves propagate in these systems with topological charge conservation. Combining this with the theoretical of excited-state phonons, we demonstrate asymmetric Klein tunneling with directional selectivity in the elastic wave carriers, and systematically investigate the performance of this tunneling. Furthermore, we design a four-port elastic waveguide based on the principle of asymmetric tunneling, which achieves exceptional directional selectivity of elastic wave signals by adjusting the polarization direction of barriers at the junctions. These studies not only extend the application of Klein tunneling in elastic wave systems but also open new research avenues for the study of elastic wave devices controlled by various external fields, showing direct application potential in elastic wave signal processing.

Half metallic ferromagnetic and transport behavior of rare earth based CdGd2(S/Se)4 spinels

Spinel chalcogen compounds have garnered significant interest in recent ages because of their promising potential in optoelectronic and thermoelectric device applications. Here, we undertake an inclusive analysis of the structural, mechanical, electronic, magnetic, optical, and transport response of CdGd2(S/Se)4 utilizing WIEN2k code based on DFT. The determination of the crystal structure's ground state and the material's thermodynamic stability is investigated through energy vs. volume plots and ∆Hf calculation. Our analysis, including Poisson (v) and Pugh (B/G) ratios, reveals the ductile nature of the studied composition. Band gap assessments are conducted using the TB-mBJ approach, revealing the semiconducting nature of investigated compounds with direct band characteristics. Specifically, calculated band gap values are 2.2 for CdGd2S4 and 1.8 eV for CdGd2Se4. Additionally, analysis of optical properties and transport response underscores the perspective of these compositions for diverse optoelectronic and thermoelectric devices.

Engineering Clock Transitions in Molecular Lanthanide Complexes.

Molecular lanthanide (Ln) complexes are promising candidates for the development of next-generation quantum technologies. High-symmetry structures incorporating integer spin Ln ions can give rise to well-isolated crystal field quasi-doublet ground states, i.e., quantum two-level systems that may serve as the basis for magnetic qubits. Recent work has shown that symmetry lowering of the coordination environment around the Ln ion can produce an avoided crossing or clock transition within the ground doublet, leading to significantly enhanced coherence. Here, we employ single-crystal high-frequency electron paramagnetic resonance spectroscopy and high-level ab initio calculations to carry out a detailed investigation of the nine-coordinate complexes, [HoIIIL1L2], where L1 = 1,4,7,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraaza-cyclododecane and L2 = F- (1) or [MeCN]0 (2). The pseudo-4-fold symmetry imposed by the neutral organic ligand scaffold (L1) and the apical anionic fluoride ion generates a strong axial anisotropy with an mJ = ±8 ground-state quasi-doublet in 1, where mJ denotes the projection of the J = 8 spin-orbital moment onto the ∼C4 axis. Meanwhile, off-diagonal crystal field interactions give rise to a giant 116.4 ± 1.0 GHz clock transition within this doublet. We then demonstrate targeted crystal field engineering of the clock transition by replacing F- with neutral MeCN (2), resulting in an increase in the clock transition frequency by a factor of 2.2. The experimental results are in broad agreement with quantum chemical calculations. This tunability is highly desirable because decoherence caused by second-order sensitivity to magnetic noise scales inversely with the clock transition frequency.

Chiral ground states of ferroelectric liquid crystals.

Ferroelectric nematic liquid crystals are formed by achiral molecules with large dipole moments. Their three-dimensional orientational order is described as unidirectionally polar. We demonstrate that the ground state of a flat slab of a ferroelectric nematic unconstrained by externally imposed alignment directions is chiral, with left- and right-handed twists of polarization. Although the helicoidal deformations and defect walls that separate domains of opposite handedness increase the elastic energy, the twists reduce the electrostatic energy and become weaker when the material is doped with ions. This work shows that the polar orientational order of molecules could trigger chirality in soft matter with no chemically induced chiral centers.

Strong Coupling of aGd3+Multilevel Spin System to an On-Chip Superconducting Resonator

We report the realization of a strong coupling between a Gd$^{3+}$ spin ensemble hosted in a scheelite (CaWO$_4$) single crystal and the resonant mode of a coplanar stripline superconducting cavity leading to a large separation of spin-photon states of 146 MHz. The interaction is well described by the Dicke model and the crystal-field Hamiltonian of the multilevel spin system. We observe a change of the crystal-field parameters due to the presence of photons in the cavity that generates a significant perturbation of the crystal ground state. Using finite-element calculations, we numerically estimate the cavity sensing volume as well as the average spin-photon coupling strength of $g_0\approx$ 620 Hz. Lastly, the dynamics of the spin-cavity states are explored via pulsed measurements by recording the cavity ring-down signal as a function of pulse length and amplitude. The results indicate a potential method to initialize this multilevel system in its ground state via an active cooling process.

Quantum skyrmion crystals and the symmetry energy of dense matter

The canonical quantization method for collective coordinates in crystalline configurations of the generalized Skyrme model is applied in order to find the quantum ground state of skyrmion crystals and study the quantum corrections to the binding energy resulting from the isospin degrees of freedom. This leads to a consistent description of asymmetric nuclear matter within the Skyrme framework and allows us to compute the symmetry energy of the skyrmionic crystal as a function of the baryon density and to compare with recent observational constraints.

CASM — A software package for first-principles based study of multicomponent crystalline solids

CASM is a software package that enables first-principles based studies of crystalline materials. It has been designed to treat coupled chemical, mechanical, vibrational, and magnetic degrees of freedom to determine ground state and finite temperature properties of crystals. The symmetry of the underlying parent crystal structure is used to enumerate perturbations of the parent crystal structure and generate derivative structures which can be input to first-principles calculations in order to explore the ground state energy landscape. CASM algorithmically constructs cluster expansions that fully couple discrete and continuous degrees of freedom, and generates highly efficient code to evaluate the cluster expansion basis functions. Widely used machine learning methods are integrated for fitting expansion coefficients to first-principle calculations. The fully parameterized cluster expansions can be combined with (kinetic) Monte Carlo methods to calculate finite temperature thermodynamic and kinetic properties. CASM Alloy Manager identifies distinct parent crystal structures in an alloy system, creating individual projects for each, and integrating the results. The integrated infrastructure facilitates the linkage between first-principles statistical mechanics predictions with higher length scale computational methods, such as phase field simulations. CASM projects are designed to be easy to share in repositories, to re-use, and to extend to include additional chemical species or types of degrees of freedom.

Unsymmetrical boron diketonates containing strong electron-donating groups as mechanochromic fluorescent solids

New π-conjugated unsymmetrical β-diketones were synthesized thanks to a modular synthetic approach involving in situ generated acylketenes through thermal degradation of 1,4-dioxin-2-ones. This method gave access to a family of new chromophores featuring either an indoline or a benzothiazole as electron-donating groups in one side and various aromatic moieties in the other side. After complexation with boron difluoride, BDK (Boron DiKetonates) compounds were obtained featuring fluorescence in non-polar solvents. These compounds were also found to be fluorescent in solid state with quantum yield up to 0.22, and their emission wavelength was very sensitive to their crystallinity. Two of these compounds were successfully recrystallized to provide small single crystals and emission spectra were recorded in crystal phase and ground state which showed mechanochromism with a spectral shift of 37 nm.

Surface waves and bulk Ruderman mode of a bosonic superfluid vortex crystal in the lowest Landau level

We determine and analyze collective normal modes of a finite disk-shaped two-dimensional vortex crystal formed in a compressible bosonic superfluid in an artificial magnetic field. Using the microscopic Gross-Pitaevskii theory in the lowest Landau level approximation, we generate vortex crystal ground states and solve the Bogoliubov-de Gennes equations for small amplitude collective oscillations. We find chiral surface waves that propagate at frequencies larger than those of the bulk Tkachenko modes. Furthermore, we study low frequency bulk excitations and identify a torsional Ruderman mode, which we find is well-described by a previously developed low-energy effective field theory.

An embedded-atom method potential for studying the properties of Fe-Pb solid-liquid interface

A new interatomic potential for Fe-Pb binary system is developed in the framework of an embedded atom model using the force-matching method. Compared with the ab initio calculations and experiment values, the developed Fe-Pb EAM potential can accurately describe the ground state, defects and liquid properties of crystal and Fe-Pb solid-liquid interface, such as equation of state, vacancy and interstitial formation energies, adsorption and escape energies, melting point, radial distribution function and density at high temperature. High accuracy and feasibility of the developed Fe-Pb EAM potential can provide the further reliable studies on the corrosion behavior of liquid Pb on steels used in complicate environment of the irradiation, high temperature, pressure in nuclear reactors.

Stability Against the Odds: The Case of Chromonic Liquid Crystals

The ground state of chromonic liquid crystals, as revealed by a number of recent experiments, is quite different from that of ordinary nematic liquid crystals: it is twisted instead of uniform. The common explanation provided for this state within the classical elastic theory of Frank demands that one Ericksen’s inequality is violated. Since in general such a violation makes Frank’s elastic free-energy functional unbounded below, the question arises as to whether the twisted ground state can be locally stable. We answer this question in the affirmative. In reaching this conclusion, a central role is played by the specific boundary conditions imposed in the experiments on the boundary of rigid containers and by a general formula that we derive here for the second variation in Frank’s elastic free energy.

Quantum fluctuations in the order parameter of quantum skyrmion crystals

Traditionally, skyrmions are treated as continuum magnetic textures of classical spins with a well-defined topological skyrmion number. Owing to their topological protection, skyrmions have attracted great interest as building blocks in future memory technology. Smaller skyrmions offer greater memory density, however, quantum effects are not negligible for skyrmions with sizes of just a few lattice constants. In this paper we study quantum fluctuations around dense skyrmion crystal ground states, and focus on the utility of a discretized order parameter for quantum skyrmions. The order parameter is found to be a useful indicator of the existence of quantum skyrmions, and captures the quantum phase transition between two distinct skyrmion phases.

Low-density phase diagram of the three-dimensional electron gas

Variational and diffusion quantum Monte Carlo methods are employed to investigate the zero-temperature phase diagram of the three-dimensional homogeneous electron gas at very low density. Fermi fluid and body-centered cubic Wigner crystal ground state energies are determined using Slater-Jastrow-backflow and Slater-Jastrow many-body wave functions at different densities and spin polarizations in finite simulation cells. Finite-size errors are removed using twist-averaged boundary conditions and extrapolation of the energy per particle to the thermodynamic limit of infinite system size. Unlike previous studies, our results show that the electron gas undergoes a first-order quantum phase transition directly from a paramagnetic fluid to a body-centered cubic crystal at density parameter $r_\text{s} = 86.6(7)$, with no region of stability for an itinerant ferromagnetic fluid. However there is a possible magnetic phase transition from an antiferromagnetic crystal to a ferromagnetic crystal at $r_\text{s}=93(3)$.

Drastic enhancement of magnetic critical temperature and amorphization in topological magnet EuSn2P2 under pressure

High pressure is an effective tool to induce exotic quantum phenomena in magnetic topological insulators by controlling the interplay of magnetic order and topological state. This work presents a comprehensive high-pressure study of the crystal structure and magnetic ground state up to 62 GPa in an intrinsic topological magnet EuSn2P2. With a combination of high resolution X-ray diffraction, 151Eu synchrotron Mössbauer spectroscopy, X-ray absorption spectroscopy, molecular orbital calculations, and electronic band structure calculations, it has been revealed that pressure drives EuSn2P2 from a rhombohedral crystal to an amorphous phase at 36 GPa accompanied by a fourfold enhancement of magnetic ordering temperature. In the pressure-induced amorphous phase, Eu ions take an intermediate valence state. The drastic enhancement of magnetic ordering temperature from 30 K at ambient pressure to 130 K at 41.2 GPa resulting from Ruderman–Kittel–Kasuya–Yosida (RKKY) interactions likely attributes to the stronger Eu–Sn interaction at high pressure. These rich results demonstrate that EuSn2P2 is an ideal platform to study the correlation of the enhanced RKKY interactions, disordered lattice, intermediate valence, and topological state.

First-principles investigations of tricarbon: From the isolated C3 molecule to a novel ultra-hard anisotropic solid

Based on crystal chemistry considerations and quantum density functional theory ground state calculations, rhombohedral rh-C3 and hexagonal h-C6 carbon allotropes are proposed and energetically calculated as new stable ultra-hard phases likewise lonsdaleite. Along the two kinds of carbon in linear C2-C1-C2 lattice, distorted tetrahedra C2(sp3) with an angle of 106.17{\deg} (smaller than ideal 109.4{\deg}) and C1(sp)-like hybridizations are inferred from charge density projections. The calculated elastic constants point to a strong anisotropy of mechanical properties of rh-C3 and h-C6 with an exceptionally large C33 values (1636 GPa and 1610 GPa, respectively), exceeding that of lonsdaleite (1380 GPa), due to the presence of aligned tricarbon units along the hexagonal c-axis. Both phases are characterized by large bulk moduli and high hardness values that are slightly less than those of lonsdaleite and diamond. Weak metallic behavior of both new phases is identified from electronic band structure calculations.

Defects in conformal crystals: Discrete versus continuous disclination models

We study the relationship between topological defect formation and ground-state 2D packings in a model of repulsions in external confining potentials. Specifically we consider screened 2D Coulombic repulsions, which conveniently parameterizes the effects of interaction range, but also serves as simple physical model of confined, parallel arrays of polyelectrolyte filaments or vortices in type II superconductors. The countervailing tendencies of repulsions and confinement to, respectively, spread and concentrate particle density leads to an energetic preference for nonuniform densities in the clusters. Ground states in such systems have previously been modeled as conformal crystals, which are composed of locally equitriangular packings whose local areal densities exhibit long-range gradients. Here we assess two theoretical models that connect the preference for nonuniform density to the formation of disclination defects, one of which assumes a continuum distributions of defects, while the second considers the quantized and localized nature of disclinations in hexagonal conformal crystals. Comparing both theoretical descriptions to numerical simulations of discrete particles clusters, we study the influence of interaction range and confining potential on the topological charge, number, and distribution of defects in ground states. We show that treating disclinations as continuously distributable well captures the number of topological defects in the ground state in the regime of long-range interactions, while as interactions become shorter range, it dramatically overpredicts the growth in total defect charge. Detailed analysis of the discretized defect theory suggests that that failure of the continuous defect theory in this limit can be attributed to the asymmetry in the preferred placement of positive vs negative disclinations in the conformal crystal ground states, as well as a strongly asymmetric dependence of self-energy of disclinations on sign of topological charge.

Interseries dipole transitions from yellow to green excitons in cuprous oxide

We study dipole interseries transitions between the yellow and green exciton series in cuprous oxide including the complex valence-band structure. To this end, we extend previous studies of the spectrum of complex green exciton resonances [P. Rommel, P. Zielinski, and J. Main, Phys. Rev. B 101, 075208 (2020)] to optical transitions between different exciton states in addition to transitions from the crystal ground state. This allows us to augment the calculations on interseries transitions using a hydrogenlike model [S. O. Kr\"uger and S. Scheel, Phys. Rev. B 100, 085201 (2019)] by a more comprehensive treatment of the valence-band structure.

Ultra-hard rhombohedral carbon by crystal chemistry and ab initio investigations

A new ultra-hard rhombohedral carbon rh-C4 (or hexagonal h-C12) is reported as derived from 3R graphite through crystal chemistry construction and ground state energy within the density functional theory. A resulting cohesive extended hexagonal three-dimensional network of h-C12 is identified as formed of C4 tetrahedra like in cubic and hexagonal diamond. The electronic band structure of rh-C4 is characteristic of insulator with Egap ​= ​4 ​eV similarly to diamond. From the energy-volume equations of state and the set of elastic constants a larger value of bulk modulus versus lonsdaleite, and the largest Vickers hardness (HV) versus both forms of diamond were revealed. The phonon band structure showing only real wave numbers further confirms the stability of the new carbon phase.

Quantum billiards with correlated electrons confined in triangular transition metal dichalcogenide monolayer nanostructures

Forcing systems through fast non-equilibrium phase transitions offers the opportunity to study new states of quantum matter that self-assemble in their wake. Here we study the quantum interference effects of correlated electrons confined in monolayer quantum nanostructures, created by femtosecond laser-induced quench through a first-order polytype structural transition in a layered transition-metal dichalcogenide material. Scanning tunnelling microscopy of the electrons confined within equilateral triangles, whose dimensions are a few crystal unit cells on the side, reveals that the trajectories are strongly modified from free-electron states both by electronic correlations and confinement. Comparison of experiments with theoretical predictions of strongly correlated electron behaviour reveals that the confining geometry destabilizes the Wigner/Mott crystal ground state, resulting in mixed itinerant and correlation-localized states intertwined on a length scale of 1 nm. The work opens the path toward understanding the quantum transport of electrons confined in atomic-scale monolayer structures based on correlated-electron-materials.