Crystal structures, phase relationships, and magnetic phase transitions of R_5M_4 compounds (R = rare earths, M = Si, Ge)

Our recent studies of the crystal structures, phase transitions, and magnetic properties of intermetallic compounds RsM4 （R = rare earths; M = Si, Ge） are reviewed briefly. First, crystal structures, phase relationships, and magnetic prop- erties of several 5：4 compounds, including Nd5 Si4-xGex, Pr5 Si4_xGex, Gds-xLaxGe4, La5 Si4, and Gd5 Sn4, are presented. In particular, the canted spin structures as well as the magnetic phase transitions in PrsSi2Ge2 and PrsGe4 investigated by neutron powder diffractions and small-angle neutron scattering are reviewed. Second, the crystal structures and magnetic properties of the most studied compounds Gds（Si,Ge）4 are summarized. The focus is on the parent compound GdsGe4, which is an amazing material exhibiting magnetic anisotropy, angular dependent spin-flop transition, metastable magnetic response, Griffiths-like phase, thermal effect under pulsed fields, antiferromagnetic and ferromagnetic resonances, pro- nounced effects of impurities, and high-field induced magnetic transitions.

Crystal structure,phase transitions,and thermodynamic properties of magnesium metavanadate(MgV_(2)O_(6))

As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile solid-state reaction by multistep-firing stoichiometric mixtures of MgO and V2O5 powder under an air atmosphere.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)occurred at 841 K and the enthalpy change was 4.37±0.04 kJ/mol.The endothermic effect at 1014 K and the enthalpy change was 26.54±0.26 kJ/mol,which is related to the incongruent melting ofβ-MgV_(2)O_(6).In situ XRD was performed to investigate phase transition of the as-prepared MgV_(2)O_(6)at high temperatures.The cell parameters obtained by Rietveld refinement indicated that it crystallizes in a monoclinic system with the C2/m space group,and the lattice parameters of a=9.280 A°,b=3.501 A°,c=6.731 A°,β=111.76°.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)was further studied by thermal kinetics,indicating that this process is controlled first by a fibril-like mechanism and then by a spherulitic-type mechanism with an increasing heating rate.Additionally,the enthalpy change of MgV_(2)O_(6)at high temperatures was measured utilizing the drop calorimetry,heat capacity was calculated and given as:Cp=208.3+0.03583T-4809000T^(−2)(298-923 K)(J mol^(−1)K^(−1)),the high-temperature heat capacity can be used to calculate Gibbs free energy of MgV_(2)O_(6)at high temperatures.

Ab initio study on crystal structure and phase stability of ZrC_(2) under high pressure

The structural stabilities and crystal evolution behaviors of the hyper stoichiometric compound ZrC_(2)(carbon rich;C/Zr> 1.0) are studied under ambient and high pressure conditions using first-principles calculations in combination with the particle-swarm optimization algorithm.Six viable structures of ZrC_(2) in P21/c,Cmmm,Cmc2_(1),P4_(2)/nmc,Immm and P6/mmm symmetries are identified.These structures are dynamically stable as their phonon spectra have no imaginary modes at zero pressure or at the selected high-pressure points.Among them,the P21/c phase represents the ground state structure,whereas P21/c,P4_(2)/nmc,Immm and P6/mmm phases are part of the phase transition series.The phase order and critical pressures of the phase transition are determined to be approximately 300 GPa according to the equation of states and enthalpy.Furthermore,the mechanical and electronic properties are investigated.The P21/c and Cmc2_(1) phases display a semi-metal nature,whereas the P4_(2)/nmc,Immm,P6/mmm and Cmmm phases exhibit a metallic nature.Moreover,the present study reveals considerable information regarding the structural,mechanical and electronic properties of ZrC_(2),thereby providing key insights into its material properties and evaluating its behavior in practical applications.

Pressure-induced phase transition and electronic structure evolution in layered semimetal HfTe_(2)

Motivated by the recent experimental work,the pressure-induced structural transition of well-known two-dimensional(2D)1T-Hf Te_(2)was investigated up to 50 GPa through the advanced CALYPSO structure search technique combined with the first-principles calculations.Our calculations suggested that the 1T-Hf Te_(2)will first transform to C2/m phase at 3.6 GPa with a volume reduction of 7.6%and then to P62m phase at 9.6 GPa with a volume collapse of 4.6%.The occurrences of 3D C2/m and P62m phases mainly originated from the enhanced Te-Te interlayer coupling and the drastic distortions of Hf-Te polyhedrons in P3m1 phase under compression.Concomitantly,the coordination number of Hf atoms increased from six in P3m1 to eight in C2/m and eventually to nine in P62m at elevated pressure.The metallic and semimetallic nature of C2/m and P62m phases were characterized,and the evidence of the reinforced covalent interactions of Te-Hf and Te-Te orbitals in these two novel high-pressure phases were manifested by the atom-projected electronic DOS and Bader charge.

Crystal structure and phase transition of 2-methoxyanilinium perchlorate-18-crown-6

A new phase transition compound,2-methoxyanilinium perchlorate-18-crown-6（1） {（oCH3OC6H4NH3）＋（18-crown-6） ClO4 },has been synthesized and separated as crystals.Differential scanning calorimetry（DSC） measurements show a pair of sharp peaks at 225 K（heating） and 210 K（cooling）,indicating the phase transition is first-order.Dielectric anomalies observed at 225 K（heating）and 210 K（cooling） further confirm the phase transition.The crystal structures determined at 298 K and123 K are both triclinic in P 1.The most distinct difference between room-temperature and lowtemperature structures is the order–disorder transition of the host 18-crown-6 molecule,which is the driving force of the phase transition.

Crystal Structure of <i>cis</i>-[PtCl₂(PyCN)₂] (PyCN = 4-Cyanopyridine) Showing Temperature Dependent Single-Crystal-to-Single-Crystal Transformation

Platinum mononuclear complex, cis-[PtCl2(PyCN)2] (1, PyCN = 4-cyanopyridine), has been synthesized and characterized by single-crystal X-ray analysis. Compound 1 crystallizes as yellow plates from the reaction of a mixture of K2PtCl4 and PyCN (=1:2) in H2O, that was left to stand at room temperature with the addition of Me2CO. Compound 1 forms the square-planar coordination geometry around the Pt atom coordinated to two Cl– ions and two pyridines of PyCN ligands in cis position. Single crystal of 1 shows the temperature dependent phase transition around 140 K, where the crystal space groups change from P21/c (high temperature) to (low temperature), which is caused by the stabilization of intermolecular interaction.

PHASE STRUCTURES AND TRANSITION BEHAVIORS OF A TRIPHENYLENE DISCOTIC LIQUID CRYSTAL

The phase behaviors and structures of a triphenylene-derived discotic liquid crystal （LC） hexa-n-octoxyl- triphenylene （C8HET） were studied using the combined techniques of differential scanning calorimetry （DSC）, wide angle X-ray diffraction （WAXD）, selected area electron diffraction （SAED） and polarized light microscopy （PLM）. Onedimensional （1D） powder WAXD results at different temperatures coupled with DSC and PLM observations revealed that the C8HET compound possessed an LC phase and three different crystalline （K3, K2 and K1） phases below the isotropic （I） melt. The I←→ LC phase transition was thermodynamically reversible and independent of the heating and cooling rates. The development and experimental observation of the three crystalline phases relied on different thermal histories. Among the three crystalline phases in CSHET, the K3 phase is the most stable phase, while the K2 and K1 phases are metastable. Note that the K1 phase only formed via a quenching process. Oh the basis of structure sensitive diffraction experiments such as 2D WAXD of oriented samples and SAED of single crystals, detailed structures and molecular packings of these four ordered phases were identified. The LC phase exhibited a hexagonal columnar phase with 2D lattice dimensions ofa = b = 2.38 nm and γ= 120°. All the three crystalline phases possess monoclinic unit cells, yet the y angle is not 90° in the cases of the K2 and the K3 phases, while in the case of the K1 phase the a angle is not 90°.

Phase transition, phase transition temperature and crystal structure of a new compound----Ca_2PdWO_6

A new compound Ca2PdWO6 has been synthesized by solid state sintering. The phase transition of this compound was investigated by means of differential thermal analysis (DTA), X-ray phase analysis, precise measurement of lattice parameters and other methods. It is discovered that the compound has a displacive phase transition of the first order at (806+5)C. The low temperature phase, a-Ca2PdWO6, belongs to orthorhombic system, with space group Pmm2. Its lattice parameters at room temperature are: a=0.79946nm, b=0.55404nm and c=0.58008nm. The measured density is Dm=6.26g/cm3, and each unit cell contains two formula weights. The high temperature phase, Ca2PdWO6, belongs to the cubic system, with space group fm3m and the lattice parameter is a = 0.810 3 nm at 860C; Z = 4. The calculated density is Dx=5.821g/cm3. The crystal structure of Ca2PdWO6 and Ca,PdWO6 was also determined by means of the X-ray polycrystal diffraction method. The factors influencing phase transition temperature are discussed in detail.

Phase transition, phase transition mechanism and crystal structure of a new compound-Ca_2FeWO_6

A new compound Ca2FeWO6 has been synthesized by solid state sintering. The phase transition of this compound was investigated by means of differential thermal analysis (DTA), X-ray powder diffraction and other methods. It is discovered that the compound has a displacive phase transition of the first order at (706±5)℃. The low temperature phase. α-Ca2FeWO6. belongs to orthorhombic system, with space group Pmm2. Its lattice parameters at room temperature are; a = 0.77051 nm, 6=0.54242nm and r = 0.551 08 nm, the measured density is Dm = 6.04g/cm3, and each unit cell contains two formula weight. The high temperature phase, β-Ca2FeWO6, belongs to the cubic system, with space group Fm3m and the lattice parameter is a = 0.780 8 nm at 750℃, z = 4. The calculated density is Dx = 5.802g/cm3, The crystal structures of α-Ca2FeWO6 and β-Ca2FeWO6 were also determined by means of the X-ray polycrystal diffraction method. The phase transition mechanism is expounded in detail.

Tunable Electronic and Magnetic Properties from Structure Phase Transition of Layered Vanadium Diselenide

The atomic geometry, structure stability, electronic and magnetic properties of VSe2 were systematically investigated based on the density functional theory（DFT）. Varying from 3D to 2D four VSe2 structures, bulk 2H-VSe2 and 1T-VSe2, monolayer H-VSe2 and T-VSe2 are all demonstrated as thermodynamically stable by lattice dynamic calculations. More interestingly, the phase transition temperature is dramatically different due to the lattice size. Finally, owing to different crystal structures, H-VSe2 is semimetallic whereas T-VSe2 is totally metallic and also they have different magnetic moments. Our main argument is that being exfoliated from bulk to monolayer, 2H-VSe2 transforms to T-VSe2, accompanied by both semimetallic-metallic transition and dramatic magnetic moment variation. Our calculations provide a novel structure phase transition and an efficient way to modulate the electronic structure and magnetic moment of layered VSe2, which suggests potential applications as high-performance functional nanomaterial.

PHASE TRANSITION AND CRYSTAL STRUCTURE OF A NEW COMPOUND-Sr_2CdWO_6

The phase transition of a new compound Sr2CdWO6 has been investigated by means ofdifferential thermal analysis （DTA）, X-ray powder diffraction, precise measurement of latticeparameters and other methods. It has been discovered that the compound has a first-orderdisplacive phase transition. The low-temperature-phase α-Sr2CdWO6 belongs to the orthor-hombic crystal system with space group Pmm2. Its lattice parameters at room temperatureare: a=8.1673A, b=5.7436A, c=5.8188A, the measured density is Dm=7.01g/cm3, andeach unit cell contains two formula weights. The high-temperature-phase β-Sr2CdWO6 be-longs to the cubic system, with space group Fm3m and lattice parameter a=8.201A at860℃, and Z=4. The crystal structures of α-Sr2CdWO6 and β-Sr2CdWO6 have been determined by meansof the X-ray polycrystal method. The phase transition mechanism and the distortion degreeare investigated.

Phase transition and crystal structure of a new compound Sr_2FeWO_6

A new compound Sr2FeWO6 has been synthesized by solid state sintering. The phase transition of this compound was investigated by means of differential scanning calorimetry (DSC), X-ray powder diffraction, precise measurement of lattice parameters and other methods. It has been discovered that the compound has a displacive phase transition of the first order at (360±5)°. The low temperature phase, α-Sr2FeWO6, belongs to tetragonal crystal system, with space group I4/m; its lattice parameters at room temperature are: a=b=0.55702 nm, and c=0.79094 ran, the measured density is Dm = 6.93 g/cm3, and each unit cell contains two formula weights. The high temperature phase, β-Sr2FeWO6, belongs to the cubic system, with space group Fm3m and the lattice parameter is a=0.7939nm at 400°; z=4. The calculated density is Dx =6.780 g/cm3. The crystal structures of α-Sr2FeWO6 and β-Sr2FeWO6 were also determined by means of the X-ray polycrystal diffraction method. The phase transition mechanism and the

Determining the structural phase transition point from the temperature of ^(40)Ca^+ Coulomb crystal

We observed the linear-to-zigzag structural phase transition of a ^40Ca^＋ crystal in a homemade linear Paul trap. The values of the total temperature of the ion crystals during the phase transition are derived using the molecular-dynamics（MD） simulation method. A series of simulations revealed that the ratio of the radial to axial secular frequencies has a dependence on the total temperature that obeys different functional forms for linear and zigzag structures, and the transition point occurs where these functions intersect; thus, the critical value of the ratio of secular frequencies that drives the structure phase transition can be derived.

Structural phase transition and transport properties in topological material candidate NaZn_(4)As_(3)

We report a comprehensive study on a layered-structure compound of NaZn_(4)As_(3),which has been predicted to be an ideal topological semimetal(TSM) candidate.It is found that NaZn_(4)As_(3) undergoes a structural transformation from high temperature rhombohedral to a low temperature monoclinic phase.The electric resistivity exhibits a metal-to-insulatorlike transition at around 100 K,and then develops a plateau at low temperature,which might be related to the protected topologically conducting surface states.Our first-principles calculation confirms further that NaZn_(4)As_(3) is a topological insulator(TI) for both different phases rather than a previously proposed TSM.The Hall resistivity reveals that the hole carriers dominate the transport properties for the whole temperature range investigated.Furthermore,an obvious kink possibly associated to the structure transition has been detected in thermopower around ~ 170 K.The large thermopower and moderate κ indicate that NaZn_(4)As_(3) and/or its derivatives can provide a good platform for optimizing and studying the thermoelectric performance.

Synthesis,Structure and Bonding Feature of New Metallic Zintl Phases RE_3Cu_3Sb_4(RE= Nd ,Sm ,Tb , Dy , Ho)

RE 3Cu 3Sb 4(RE=Nd, Sm, Tb, Dy, Ho) was synthesized by arc melting method and their crystal structures were characterized by powder X ray method. The compounds crystallize in cubic system, Y 3Au 3Sb 4 type, space group I43d (No.220), Pearson code cI40. The unit cell parameters are: Nd 3Cu 3Sb 4: a =0 96749(1) nm, V =0 90561(3) nm 3; Sm 3Cu 3Sb 4: a =0 96145(1) nm, V =0 88875(3) nm 3; Tb 3Cu 3Sb 4: a =0 95362(1) nm, V =0 86721(3) nm 3; Dy 3Cu 3Sb 4: a =0 95088(1) nm, V =0 85975(3) nm 3; Ho 3Cu 3Sb 4: a =0 9488(2) nm, V =0 8541(5) nm 3; Z =4. The structures are characterized by covalent bonded Cu Sb tetrahedra which form three dimensional networks by sharing corners. The rare earth atoms are distributed in the cages. The formula with the charge balance can be written as RE 3+ 3Cu 1+ 3Sb 3- 4 which are metallic Zintl phases having the weak metallic conductivity. The bonds have typical transitional features. General atomic coordination environment rules are followed. The unit cell parameters show the lanthanide contraction.

Regulation of the order-disorder phase transition in a Cs_(2)NaFeCl_(6) double perovskite towards reversible thermochromic application

Multifunctional lead-free double perovskites demonstrate remarkable potential towards applications in various fields.Herein,an environmentally-friendly,low-cost,high-throughput Cs_(2)NaFeCl_(6) single crystal with exceedingly high thermal stability is designed and grown.It obtains a cubic lattice system in the temperature range of 80-500 K,accompanied by a completely reversible chromatic variation ranging from yellow to black.Importantly,the intriguing thermochromism is proved to own extremely high reproducibility(over 1000 cycles)without a hysteretic effect,originating from its structural flexibility that including(i)the noteworthy distortion/deformation of[NaCl_(6)]5−and[FeCl_(6)]3−octahedra;(ii)order-disorder arrangement transition of[NaCl_(6)]5−and[FeCl6]3−octahedra as the function of temperature.This study paves the way towards a new class of smart windows and camouflage coatings with an unprecedented colour range based on a Cs_(2)NaFeCl_(6) perovskite.

Structural phase transition, precursory electronic anomaly, and strong-coupling superconductivity in quasi-skutterudite (Sr1-xCax)3Ir4Sn13 and Ca3Rh4Sn13

The interplay between superconductivity and structural phase transition has attracted enormous interest in recent years. For example, in Fe-pnictide high temperature superconductors, quantum fluctuations in association with structural phase transition have been proposed to lead to many novel physical properties and even the superconductivity itself. Here we report a finding that the quasi-skutterudite superconductors （Sr1-xCax）3Ir4Sn13 （x = 0, 0.5, 1） and Ca3Rh4Snl3 show some unusual properties similar to the Fe-pnictides, through 119Sn nuclear magnetic resonance （NMR） measurements. In （Sr1-xCax）3Ir4Sn13, the NMR linewidth increases below a temperature T＊ that is higher than the structural phase transition temperature Ts. The spin-lattice relaxation rate （1/T1 ） divided by temperature （T）, 1/TI T and the Knight shift K increase with decreasing T down to T＊, but start to decrease below T＊, and followed by more distinct changes at Ts. In contrast, none of the anomalies is observed in Ca3Rh4Sn13 that does not undergo a structural phase transition. The precursory phenomenon above the structural phase transition resembles that occurring in Fe-pnictides. In the superconducting state of Ca3Ir4Sn13, 1/T1 decays as exp（-△/kBT） with a large gap △ = 2.21kBTc, yet without a Hebel-Slichter coherence peak, which indicates strong-coupling superconductivity. Our results provide new insight into the relationship between superconductivity and the electronic-structure change associated with structural phase transition.

Precessing Ball Solitons as Self-Organizing Systems during a Phase Transition in a Ferromagnet

Precessing ball solitons (PBS) in a ferromagnet during the first order phase transition is induced by a magnetic field directed along the axis of anisotropy, while the action of the periodic field perpendicular to the main magnetic field has been analyzed. Under these conditions, the characteristics of arising equilibrium PBS are uniquely determined by the frequency of the periodic field, but the solitons with other frequencies are impossible. For such structure, the entropy increase connected with dissipation is compensated by the decrease of the entropy due to the external periodic field. It is shown that the equilibrium PBS are essentially the “self-organizing systems” that can arise spotaneously in a metastable state of ferromagnet.

Structural changes concurrent with ferromagnetic transition

Ferromagnetic transition has generally been considered to involve only an ordering of magnetic moment with no change in the host crystal structure or symmetry, as evidenced by a wealth of crystal structure data from conventional X-ray diffractometry （XRD）. However, the existence of magnetostriction in all known ferromagnetic systems indicates that the magnetic moment is coupled to the crystal lattice; hence there is a possibility that magnetic ordering may cause a change in crystal structure. With the development of high-resolution synchrotron XRD, more and more magnetic transitions have been found to be accompanied by simultaneous structural changes. In this article, we review our recent progress in understand- ing the structural change at a ferromagnetic transition, including synchrotron XRD evidence of structural changes at the ferromagnetic transition, a phenomenological theory of crystal structure changes accompanying ferromagnetic transitions, new insight into magnetic morphotropic phase boundaries （MPB） and so on. Two intriguing implications of non-centric symmetry in the ferromagnetic phase and the first-order nature of ferromagnetic transition are also discussed here. In short, this review is intended to give a self-consistent and logical account of structural change occurring simultaneously with a ferromagnetic transition, which may provide new insight for developing highly magneto-responsive materials.