High‐pressure polarized Raman spectra of Gd2(MoO4)3: phase transitions and amorphization

Polarized Raman spectra of a single crystal of gadolinium molybdate [Gd₂(MoO₄)₃] were obtained between 1 atm and 7 GPa. Using a mixture of alcohols as the pressure‐transmitting medium, YY, ZZ, XY components of scattering matrices were measured. The ZZ spectra were also obtained in argon. Five phase transitions and amorphization were identified. The first and second transitions are reversible, while amorphization is not. In alcohol, amorphization is observed above 6.5 GPa. With argon as the pressure‐transmitting medium, amorphization is progressive and begins above 3 GPa. The spectral changes with pressure affect the high wavenumber bands attributed to symmetric and antisymmetric MoO₄ stretching modes as well as the very low wavenumber modes such as librations of the tetrahedra. This means that both short‐range and long‐range organizations of the tetrahedra are involved in these phase transitions. The amorphization mechanism and its dependence on the pressure‐transmitting medium are discussed, and the steric hindrance between polyhedra is believed to be the most relevant mechanism. The TO and LO low wavenumber modes of A₁ symmetry, observed in the Y(ZZ)Y and Z(YY)Z geometries, respectively, below 50 cm⁻¹, soften continuously through the first three phases when increasing pressure. The strong A₂ mode observed in the Z(XY)Z spectra exhibits the same anomalous behavior by decreasing from 53 to 46 cm⁻¹ at 2 GPa. The softening of these modes is related to the orientation change of tetrahedra observed by ab initio calculations when the volume of the cell is decreased. These orientation changes can explain the wavenumber decrease of the Mo O stretching modes above 2 GPa, which indicates an increase of Mo coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

Temperature‐induced phase transformations in Na2WO4 and Na2MoO4 crystals

Temperature‐dependent Raman studies on Na₂WO₄and Na₂MoO₄ crystals were performed in order to obtain information on structural changes induced by temperature evolution. The stability of the cubic phase of Na₂WO₄and Na₂MoO₄crystals was assessed and our results indicate that this phase is stable in the 8–823 K and 15–773 K ranges for Na₂WO₄ and Na₂MoO₄, respectively. The crystal of Na₂WO₄ shows a phase transition occurring at 833 K. Na₂MoO₄undergoes a sequence of three phase transitions, which were observed at 783–803, 823–913 and 943–950 K. In both crystals, a strong first‐order phase transition occurs as indicated by the behavior of the Raman modes: the Raman bands split and new bands appear below 100 cm⁻¹. These transitions are connected with tilting and/or rotations of the WO₄and MoO₄ tetrahedra, which leads to a disorder at the WO₄and MoO₄ sites. Copyright © 2010 John Wiley & Sons, Ltd.     

Phase transition and thermal expansion property of Cr_(2-x)Zr_(0.5x)Mg_(0.5x)Mo_3O_(12) solid solution

Compounds with the formula Cr2-xZr0.5xMg0.5xMo3O12（x = 0.0, 0.3, 0.5, 0.9, 1.3, 1.5, 1.7, 1.9） are synthesized, and the effects of Zr4＋ and Mg2＋ co-incorporation on the phase transition, thermal expansion, and Raman mode are investigated. It is found that Cr2-xZr0.5xMg0.5xMo3O12 crystallize into monoclinic structures for x 〈 1.3 and orthorhombic structures for x _〉 1.5 at room temperature. The phase transition temperature from a monoclinic to an orthorhombic structure of Cr2Mo3O12 can be reduced by the partial substitution of （ZrMg）6＋ for Cr3＋. The overall linear thermal expansion coefficient decreases with the increase of the （ZrMg）6＋ content in an orthorhombic structure sample. The co-incorporation of Zr4＋ and Mg2＋ in the lattice results in the occurrence of new Raman modes and the hardening of the symmetric vibrational modes, which are attributed to the MoO4 tetrahedra sharing comers with ZrO6/MgO6 octahedra and to the strengthening of Mo-O bonds due to less electronegativities of Zr4＋ and Mg2＋ than Cr3＋, respectively.     

In situ Raman and photoluminescence study on pressure‐induced phase transition in C60 nanotubes

Single crystalline C₆₀ nanotubes having face‐centered‐cubic structure with diameters in the nanometer range were synthesized by a solution method. In situ Raman and photoluminescence spectroscopy under high pressure were employed to study the structural stabilities and transitions of the pristine C₆₀ nanotubes. A phase transition, probably because of the orientational ordering of C₆₀ molecules, from face‐centered‐cubic structure to simple cubic structure occurred at the pressure between 1.46 and 2.26 GPa. At above 20.41 GPa, the Raman spectrum became very diffuse and lost its fine structure in all wavenumber regions, and only two broad and asymmetry peaks initially centered at 1469 and 1570 cm^–1 were observed, indicating an occurrence of amorphization. This amorphous phase remained to be reversible until 31.1 GPa, and it became irreversible to the ambient pressure after the pressure cycle of 34.3 GPa was applied. Copyright © 2012 John Wiley & Sons, Ltd.     

High‐pressure studies of the micro‐Raman spectra of iron cyanide complexes: Prussian blue (Fe4[Fe(CN)6]3), potassium ferricyanide (K3[Fe(CN)6]), and sodium nitroprusside (Na2[Fe(CN)5(NO)]·2H2O)

The pressure dependences of the peaks observed in the micro‐Raman spectra of Prussian blue (Fe₄[Fe(CN)₆]₃), potassium ferricyanide (K₃[Fe(CN)₆]), and sodium nitroprusside (Na₂[Fe(CN)₅(NO)]·2H₂O) have been measured up to 5.0 GPa. The vibrational modes of Prussian blue appearing at 201 and 365 cm⁻¹ show negative dν/dP values and Grüneisen parameters and are assigned to the transverse bending modes of the Fe C N Fe linkage which can contribute to a negative thermal expansion behavior. A phase transition occurring between 2.0 and 2.8 GPa in potassium ferricyanide is shown by changes in the spectral region 150–700 cm⁻¹. In the spectra of the nitroprusside ion, there are strong interactions between the FeN stretching mode and the FeNO bending and the axial CN stretching modes. The pressure dependence of the NO stretching vibration is positive, 5.6 cm⁻¹ GPa⁻¹, in contrast to the negative behavior in the iron(II)‐meso‐tetraphenyl porphyrinate complex. Copyright © 2011 John Wiley & Sons, Ltd.     

Pressure-induced structural and electronic transition in KTb(MoO4)2 through Raman and optical studies

Raman and optical absorption studies under pressure have been conducted on KTb(MoO₄)₂ up to 35.5 GPa. A phase transformation occurs at 2.7 GPa when the crystal is pressurized at ambient temperature in a hydrostatic pressure medium. The sample changes to a deep yellow color at the transition and visibly contracts in theα-axis direction. The color shifts to red on further pressure increase. The Raman spectral features and the X-ray powder pattern change abruptly at the transition indicating a structural change. The pressure-induced transition appears to be a property of the layer-type alkali rare earth dimolybdates. However, the color change at the transition in KTb(MoO₄)₂ is rather unusual and is attributed to a valence change in Tb initiated by the structural transition and consequent intervalence charge transfer between Tb and Mo.In situ high pressure X-ray diffraction data suggest that phase II could be orthorhombic with a unit cell having 3 to 4% smaller volume than that of phase I.     

Pressure‐induced phase transitions in palmitic acid: C form

In this article, we report a high‐pressure Raman spectroscopy study of palmitic acid (PA, C form) from ambient pressure up to 21 GPa. The effects of hydrostatic pressure on the vibrational spectrum of PA are reported, and the data show that PA experiences a rich sequence of phase transformations. These changes in the crystal structure occur gradually as the pressure increases and they are related to the highly flexible crystalline structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Pressure-induced amorphization of Gd2(MoO4)3: A high pressure Raman investigation

High pressure Raman spectroscopic studies on Gd₂(MoO₄)₃(GMO) have been carried out at ambient temperature in the diamond cell to 10 GPa hydrostatic pressure. These experiments have revealed pressure-induced phase transitions in GMO near 2 GPa and 6.0 GPa. The first transition is from Pba2(β′) phase to another undetermined crystalline phase, designated as phase II, and the second transition is to an amorphized state. On releasing pressure there is a partial reversion to the crystalline state. The Raman data indicate that the amorphization is due to disordering of the MoO₄ tetrahedral units. Further, it is inferred from the nature of the Raman bands in the amorphized material that the Mo-O bond lengths and bond angles have a range of values, instead of a few set values. The results of the present study as well as previous high pressure-high temperature quenching experiments strongly support that pressure-induced amorphization in GMO is a consequence of the kinetically impededβ toα phase transition. The system in frustration becomes disordered. The rare earth trimolybdates crystallizing in theβ′ structure are all expected to undergo similar pressure-induced amorphization.     

Raman spectroscopy study of Na2MoO4·2H2O and Na2MoO4 under hydrostatic pressure

Raman spectroscopy measurements of polycrystalline Na₂MoO₄·2H₂O (NMHO) and Na₂MoO₄ (NM) under hydrostatic pressure (from 0 to 10 GPa) were performed. This study allowed us to monitor the stretching and bending vibrations of MoO₄ ions as well as the translational modes as a function of pressure. The pressure dependence of the wavenumbers of the modes indicates that the Na₂MoO₄·2H₂O undergoes two phase transitions at about ∼3 and ∼4 GPa. When releasing pressure, we have observed that the original spectrum is recovered, thereby pointing to a reversible process. The Na₂MoO₄ (NM) starting phase was found to be stable up to 10 GPa. The pressure‐dependent Raman data for NM did not reveal any structural modification. The influence of the pressure‐transmitting medium on the phase transitions is also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Pressure evolution of two polymorphs of Tb 2(MoO 4)3

We have studied the high pressure behavior of the α and β^′-phases of Tb ₂(MoO ₄)₃ using a combination of powder X-ray diffraction and ab initio calculations. The α-Tb ₂(MoO ₄)₃ phase did not undergo any structural phase transition in the pressure range from 0 up to the maximum experimental pressure of 21 GPa. We observed line broadening of the diffraction patterns at pressures above 7 GPa, which may be due to non-hydrostatic conditions. The complete amorphization of the sample was not reached in the pressure range studied, as expected from previous Raman studies. The behavior under pressure of the β^′-Tb ₂(MoO ₄)₃ phase is similar to that of other rare-earths trimolybdates with the same structure at room temperature. A phase transition was observed at 2 GPa. The new phase, which can be identified as the δ-phase, has never been completely characterized by diffraction studies. A tentative indexation has been performed and good refined cell parameters were obtained. We detect indications of amorphization of the δ-Tb ₂(MoO ₄)₃ phase at 5 GPa.     

Fe2-xYxMo3O12系列材料的相变及负膨胀性研究

本文对Fe2-xYx(MoO4)3(x=0.0,0.2,0.4,0.5,0.6,0.8,1.0,1.2,1.4,1.6,1.8,2.0)系列材料的相变及负膨胀性能进行了研究.通过对Fe2-xYx( MoO4)3系列材料的XRD和拉曼谱的分析发现,当x≤0.4时Fe2-xYxMo3O12在常温下是单斜结构;当x≥0.5时...     

A2( MoO4)3(A=Al,Cr,Fe)结构与相变的Raman光谱研究

用XRD、Raman光谱和DSC研究了Al2 (MoO4)3、Cr2( MoO4)3和Fe2 (MoO4)3的结构与相变.Al2(MoO4)3、Cr2 (MoO4)3和Fe2 (MoO4)3在室温下为单斜相,分别在483 K、673 K和783 K附近转变为正交相.发现MO4四面体的对称和反对称伸缩振动模的频率和相对强...     

The phase transition,hygroscopicity, and thermal expansion properties of Yb_2-xAl_xMo₃O₁₂

Materials with the formula Yb 2-xAlxMo3O12(x =0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9, 1.0, 1.1, 1.3, 1.5, and 1.8) were synthesized and their structures, phase transitions, and hygroscopicity investigated using X-ray powder diffrac- tion, Raman spectroscopy, and thermal analysis. It is shown that Yb2-xAlxMo3O12 solid solutions crystallize in a single monoclinic phase for 1.7 ≤ x ≤ 2.0 and in a single orthorhombic phase for 0.0 ≤ x ≤ 0.4, and exhibit the characteristics of both monoclinic and orthorhombic structures outside these compositional ranges. The monoclinic to orthorhombic phase transition temperature of Al2Mo3O12 can be reduced by partial substitution of Al 3+ by Yb3+, and the Yb2-x AlxMo3O12 (0.0 < x ≤ 2.0) materials are hydrated at room temperature and contain two kinds of water species. One of these interacts strongly with and hinders the motions of the polyhedra, while the other does not. The partial substitution of Al3+ for Yb3+ in Yb2Mo3O12 decreases its hygroscopicity, and the linear thermal expansion co- efficients after complete removal of water species are measured to be 9.1×10 6 /K, 5.5×10 6 /K, 5.74×10 6 /K, and 9.5 × 10 6 /K for Yb1.8 Al0.2 (MoO4)3 , Yb1.6Al0.4 (MoO4 )3, Yb0.4 Al1.6 (MoO4)3 , and Yb 0.2Al1.8 (MoO4)3 , respectively.     

Rotational disorder in 2‐piperidyl‐5‐nitro‐6 ‐methylpyridine: structural phase transition and its vibrational characteristics

X‐ray diffraction (XRD) studies have shown that 2‐piperidyl‐5‐nitro‐6‐methylpyridine, C₁₁H₁₅N₃O₂, undergoes a structural phase transition at T = 240 K. The room temperature structure is tetragonal, space group I4₁/a, with the unit‐cell dimensions a = 13.993(2) and c = 23.585(5) Å. The pyridine ring takes trans conformation with respect to the piperidine unit. While pyridine is well ordered, the piperidine moiety shows apparent disorder resulting from a libration about the linking N C bond. The low‐temperature phase is monoclinic, space group I2/a. Contraction of the unit‐cell volume by 2.3% at 170 K enables the C H···O linkage between the molecules of the neighbouring stacks. As result, the asymmetric unit becomes bi‐molecular. The thermal librations of the piperidine and methyl groups become considerably reduced at 170 K and nearly fully reduced at about 100 K. The IR spectra and polarised Raman spectra agree with the X‐ray structure and confirm the disorder effect on the piperidine ring. The assignment of the bands observed was made on the basis of DFT chemical quantum calculations. Copyright © 2008 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman scattering studies of Na2MoO4

The mode assignment of the cubic phase of anhydrous Na₂MoO₄ was carried out on the basis of lattice dynamic calculation using the classical rigid‐ion model. Temperature‐dependent studies indicate that this crystal remains in the cubic structure in the 15–773 K range and undergoes a phase transition at around 783 K. The behavior of the Raman modes indicates that this transition is strongly first‐order in nature and the phase above 773 K may have an orthorhombic symmetry. This transition is connected with tilting and/or rotations of the MoO₄ tetrahedra, which lead to a disorder at the MoO₄ sites. Our results give also evidence that the Mo O bond lengths decrease in the high‐temperature phase. Copyright © 2008 John Wiley & Sons, Ltd.     

Near-zero thermal expansion of In_(2(1-x))(HfMg)_xMo_3O_(12) with tailored phase transition

Solid solutions of In_(2(1-x)(HfMg)_xMo_3O_(12) are synthesized by solid state reaction with the aim to reduce the phase transition temperature of In_2Mo_3O_(12) and improve its thermal expansion property.The effects of(HfMg)~(6+) incorporation on the phase transition and thermal expansion are investigated.It is shown that the monoclinic-to-orthorhombic phase transition temperature obviously decreases and the coefficient of thermal expansion(CTE) of the orthorhombic becomes less negative and approaches to zero with increasing the content of(HfMg)~(6+).A near zero thermal expansion covering the case at room temperature(RT) is achieved for the solid solutions with x ≥ 0.85,implying potential applications of this material in many fields.     

Synthesis and X‐ray structures of unexpected 2‐O‐(5‐deoxy‐1,2‐O‐isopropylidene‐α‐D‐glucofuranos‐5‐yloxy)quinoxalines

Reaction of 3‐methyl‐2(1H)‐quinoxalinone ( 4) and 2(1H)‐quinoxalinone ( 5) with 5,6‐anhydro‐1,2‐O‐isopropylidene‐ α‐D ‐glucofuranose 6 gives the unexpected O‐glucoquinoxalines derivatives by the intermediary novel intramolecular rearrangement of 5,6‐anhydro‐1,2‐O‐isopropylidene‐α‐D ‐glucofuranose to the corresponding 3,6‐anhydro form. The obtained O‐glucoquinoxalines 7,8 were identified by NMR spectroscopy. The X‐ray crystal structures have been determined at room temperature. Moreover, a solid–solid phase transition has been detected at 198.9 K for O‐glucoquinoxalines 7 and the structure of the low‐temperature phase has been solved at 188 K. Copyright © 2009 John Wiley & Sons, Ltd.     

Pressure induced magnetic and semiconductor–metal phase transitions in Cr_2MoO_6

We investigate magnetic ordering and electronic structures of Cr_2MoO_6under hydrostatic pressure. To overcome the band gap problem, the modified Becke and Johnson exchange potential is used to investigate the electronic structures of Cr_2MoO_6. The insulating nature at the experimental crystal structure is produced, with a band gap of 1.04 eV, and the magnetic moment of the Cr atom is 2.50 μB, compared to an experimental value of about 2.47 μB. The calculated results show that an antiferromagnetic inter-bilayer coupling–ferromagnetic intra-bilayer coupling to a ferromagnetic inter-bilayer coupling–antiferromagnetic intra-bilayer coupling phase transition is produced with the pressure increasing. The magnetic phase transition is simultaneously accompanied by a semiconductor–metal phase transition. The magnetic phase transition can be explained by the Mo–O hybridization strength, and ferromagnetic coupling between two Cr atoms can be understood by empty Mo-d bands perturbing the nearest O-p orbital.     

Pressure‐induced anomalous phase transformation in nano‐crystalline dysprosium sesquioxide

The phase transformation in nano‐crystalline dysprosium sesquioxide (Dy₂O₃) under high pressures is investigated using in situ Raman spectroscopy. The material at ambient was found to be cubic in structure using X‐ray diffraction (XRD) and Raman spectroscopy, while atomic force microscope (AFM) showed the nano‐crystalline nature of the material which was further confirmed using XRD. Under ambient conditions the Raman spectrum showed a predominant cubic phase peak at 374 cm⁻¹, identified as F_g mode. With increase in the applied pressure this band steadily shifts to higher wavenumbers. However, around a pressure of about 14.6 GPa, another broad band is seen to be developing around 530 cm⁻¹ which splits into two distinct peaks as the pressure is further increased. In addition, the cubic phase peak also starts losing intensity significantly, and above a pressure of 17.81 GPa this peak almost completely disappears and is replaced by two strong peaks at about 517 and 553 cm⁻¹. These peaks have been identified as occurring due to the development of hexagonal phase at the expense of cubic phase. Further increase in pressure up to about 25.5 GPa does not lead to any new peaks apart from slight shifting of the hexagonal phase peaks to higher wavenumbers. With release of the applied pressure, these peaks shift to lower wavenumbers and lose their doublet nature. However, the starting cubic phase is not recovered at total release but rather ends up in monoclinic structure. The factors contributing to this anomalous phase evolution would be discussed in detail. Copyright © 2010 John Wiley & Sons, Ltd.