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The liquid-liquid transition (LLT), in which a single-component liquid transforms into another one via a first-order phase transition, is an intriguing phenomenon that has changed our perception of the liquid state. LLTs have been predicted from computer simulations of water1,2, silicon3, carbon dioxide4, carbon5, hydrogen6 and nitrogen7. Experimental evidence has been found mostly in supercooled (that is, metastable) liquids such as Y2O3-Al2O3 mixtures8, water9 and other molecular liquids10-12. However, the LLT in supercooled liquids often occurs simultaneously with crystallization, making it difficult to separate the two phenomena13. A liquid-liquid critical point (LLCP), similar to the gas-liquid critical point, has been predicted at the end of the LLT line that separates the low- and high-density liquids in some cases, but has not yet been experimentally observed for any materials. This putative LLCP has been invoked to explain the thermodynamic anomalies of water1. Here we report combined in situ density, X-ray diffraction and Raman scattering measurements that provide direct evidence for a first-order LLT and an LLCP in sulfur. The transformation manifests itself as a sharp density jump between the low- and high-density liquids and by distinct features in the pair distribution function. We observe a non-monotonic variation of the density jump with increasing temperature: it first increases and then decreases when moving away from the critical point. This behaviour is linked to the competing effects of density and entropy in driving the transition. The existence of a first-order LLT and a critical point in sulfur could provide insight into the anomalous behaviour of important liquids such as water.
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Structural transformation of hot dense water ice is investigated by combining synchrotron x-ray diffraction and a laser-heating diamond anvil cell above 25 GPa. A transition from the body-centered-cubic (bcc) to face-centered-cubic (fcc) oxygen atoms sublattices is observed from 57 GPa and 1500 K to 166 GPa and 2500 K. That is the structural signature of the transition to fcc superionic (fcc SI) ice. The sign of the density discontinuity at the transition is obtained and a phase diagram is disclosed, showing an extended fcc SI stability field. Present data also constrain the stability field of the bcc superionic (bcc SI) ice up to 100 GPa at least. The current understanding of warm dense water ice based on ab initio simulations is discussed in the light of present data.
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Synchrotron x-ray diffraction measurements of nitrogen are performed up to 120 GPa to determine the melting curve and the structural changes of the solid and liquid phases along it. The melting temperature exhibits a monotonic increase up to the triple point where the epsilon molecular solid, the cubic gauche covalent solid, and the fluid meet at 116 GPa, 2080 K. Above, the stability of the cubic gauche phase induces a sharp increase of the melting curve. The structural data on liquid nitrogen show that the latter remains molecular over the whole probed domain, which contradicts the prediction of a liquid-liquid transition at 88 GPa, 2000 K. These findings thus largely revisit the phase diagram of hot dense nitrogen and challenge the current understanding of this model system.
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Black phosphorus (bP) is a crystalline material that can be seen as an ordered stacking of two-dimensional layers, which results in outstanding anisotropic physical properties. The knowledge of its pressure (P)-temperature (T) phase diagram, and in particular, of its melting curve is fundamental for a better understanding of the synthesis and stability conditions of this element. Despite the numerous studies devoted to this subject, significant uncertainties remain regarding the determination of the position and slope of its melting curve. Here we measured the melting curve of bP in an extended P, T region from 0.10(3) to 5.05(40) GPa and from 914(25) to 1788(70) K, using in situ high-pressure and high-temperature synchrotron X-ray diffraction. We employed an original metrology based on the anisotropic thermoelastic properties of bP to accurately determine P and T. We observed a monotonic increase of the melting temperature with pressure and the existence of two distinct linear regimes below and above 1.35(15) GPa, with respective slopes of 348 ± 21 and of 105 ± 12 K·GPa-1. These correspond to the melting of bP toward the low-density liquid and the high-density liquid, respectively. The triple point at which solid bP and the two liquids meet is located at 1.35(15) GPa and 1350(25) K. In addition, we have characterized the solid phases after crystallization of the two liquids and found that, while the high-density liquid transforms back to solid bP, the low-density liquid crystallizes into a more complex, partly crystalline and partly amorphous solid. The X-ray diffraction pattern of the crystalline component could be indexed as a mixture of red and violet P.
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Hexagonal boron nitride (hBN) and black phosphorus (bP) are crystalline materials that can be seen as ordered stackings of two-dimensional layers, which lead to outstanding anisotropic physical properties. Knowledge of the thermal equations of state of hBN and bP is of great interest in the field of 2D materials for a better understanding of their anisotropic thermo-mechanical properties and exfoliation mechanism towards the preparation of important single-layer materials like hexagonal boron nitride nanosheets and phosphorene. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the thermoelastic parameters of hBN and bP. Here, we report accurate thermal expansion and compressibility measurements along the individual crystallographic axes, using in situ high-temperature and high-pressure high-resolution synchrotron X-ray diffraction. In particular, we have quantitatively determined the subtle variations of the in-plane and volumetric thermal expansion coefficients and compressibility parameters by subjecting these materials to hydrostatic conditions and by collecting a large number of data points in small pressure and temperature increments. In addition, based on the anisotropic behavior of bP, we propose the use of this material as a sensor for the simultaneous determination of pressure and temperature in the range of 0-5 GPa and 298-1700 K, respectively.
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The structure of polymeric carbon dioxide (CO2-V) has been solved using synchrotron x-ray powder diffraction, and its evolution followed from 8 to 65 GPa. We compare the experimental results obtained for a 100% CO2 sample and a 1 mol % CO2/He sample. The latter allows us to produce the polymer in a pure form and study its compressibility under hydrostatic conditions. The high quality of the x-ray data enables us to solve the structure directly from experiments. The latter is isomorphic to the ß-cristobalite phase of SiO2 with the space group I42d. Carbon and oxygen atoms are arranged in CO4 tetrahedral units linked by oxygen atoms at the corners. The bulk modulus determined under hydrostatic conditions, B0=136(10) GPa, is much smaller than previously reported. The comparison of our experimental findings with theoretical calculations performed in the present and previous studies shows that density functional theory very well describes polymeric CO2.
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We present an extended investigation of phase I of carbon dioxide by x-ray diffraction and spectroscopic techniques at simultaneous high pressure and high temperature, up to 12 GPa and 800 K. Based on the present and literature data, we show that a Mie-Grüneisen-Debye model reproduces within experimental uncertainties the equation of state of CO(2) over the entire range of stability of phase I. Using infrared and Raman spectroscopy, we have determined the frequencies of the zone-center lattice modes as a function of pressure and temperature. We have then extracted the volume and temperature dependencies of the optical lattice mode frequencies and their respective Grüneisen parameters. We find a large difference between the thermodynamic Grüneisen parameter obtained from the P-V-T data and those associated with the optical lattice modes. This suggests, within the quasiharmonic approximation, that acoustic modes have a dominant contribution to the anharmonicity of the system.
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The compression of ammonium azide (AA) has been considered to be a promising route for producing high energy-density polynitrogen compounds. So far though, there is no experimental evidence that pure AA can be transformed into polynitrogen materials under high pressure at room temperature. We report here on high pressure (P) and temperature (T) experiments on AA embedded in N2 and on pure AA in the range 0-30 GPa, 300-700 K. The decomposition of AA into N2 and NH3 was observed in liquid N2 around 15 GPa-700 K. For pressures above 20 GPa, our results show that AA in N2 transforms into a new crystalline compound and solid ammonia when heated above 620 K. This compound is stable at room temperature and on decompression down to at least 7.0 GPa. Pure AA also transforms into a new compound at similar P-T conditions, but the product is different. The newly observed phases are studied by Raman spectroscopy and X-ray diffraction and compared to nitrogen and hydronitrogen compounds that have been predicted in the literature. While there is no exact match with any of them, similar vibrational features are found between the product that was obtained in AA + N2 with a polymeric compound of N9H formula.
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Black phosphorus (bP) is a crystalline material which can be seen as an ordered stacking of two-dimensional layers, referred to as phosphorene. The knowledge of the linear thermal expansion coefficients (LTECs) of bP is of great interest in the field of 2D materials for a better understanding of the anisotropic thermal properties and exfoliation mechanism of this material. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the LTECs of bP. Here, we report accurate thermal expansion measurements along the three crystallographic axes using in situ high temperature X-ray diffraction. From the progressive reduction of the diffracted intensities with temperature, we monitored the loss of the crystal structure of bP across the investigated temperature range, evidencing two thermal expansion regimes at temperature below and above 706 K. Below 706 K, a strong out-of-plane anisotropy can be observed, while at temperatures above 706 K a larger thermal expansion occurs along the a crystallographic direction. From our data and by taking advantage of ab initio optimization, we propose a detailed anisotropic thermal expansion mechanism of bP, which leads to an inter- and intra-layer destabilization. An interpretation of it, based on the high T perturbation of the stabilizing sp orbital mixing effect, is provided, consistent with the high pressure data.
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The existence of "intermediate bonding states" in solid CO2, separating the low-pressure molecular phases from the high-pressure polymeric forms, has been the matter of a long-standing debate. Here we determine the structure of CO2-IV using x-ray diffraction of single crystals grown inside a diamond anvil cell at 11.7 GPa and 830 K. It is rhombohedral, space group R3[over ]c, and is composed of individual, linear CO2 molecules with bond lengths of 1.155(2) A at 15 GPa. This shows that CO2 remains a purely molecular solid in this P-T range, and thus invalidates the intermediate bonding state scenario. First-principles calculations confirm the stability of the proposed structure and match very well observations, including the Raman and IR spectra. Furthermore, these results evidence a striking similarity between the high-pressure polymorphs of solid CO2 and N2.
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Angle dispersion X-ray diffraction (AXDX) experiments on nitromethane single crystals and powder were performed at room temperature as a function of pressure up to 19.0 and 27.3 GPa, respectively, in a membrane diamond anvil cell (MDAC). The atomic positions were refined at 1.1, 3.2, 7.6, 11.0, and 15.0 GPa using the single-crystal data, while the equation of state (EOS) was extended up to 27.3 GPa, which is close to the nitromethane decomposition threshold pressure at room temperature in static conditions. The crystal structure was found to be orthorhombic, space group P2(1)2(1)2(1), with four molecules per unit cell, up to the highest pressure. In contrast, the molecular geometry undergoes an important change consisting of a gradual blocking of the methyl group libration about the C-N bond axis, starting just above the melting pressure and completed only between 7.6 and 11.0 GPa. Above this pressure, the orientation of the methyl group is quasi-eclipsed with respect to the NO bonds. This conformation allows the buildup of networks of strong intermolecular O...H-C interactions mainly in the bc and ac planes, stabilizing the crystal structure. This structural evolution determines important modifications in the IR and Raman spectra, occurring around 10 GPa. Present measurements of the Raman and IR vibrational spectra as a function of pressure at different temperatures evidence the existence of a kinetic barrier for this internal rearrangement.
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The structural transformations occurring to water from the low- to the high-density regimes have been studied by classical molecular dynamics calculations. The local structure is analyzed through a proper choice of the relevant orientational distribution functions. This approach sheds light on the key role played by the interstitial molecules in the second coordination shell and identifies a clear structural fingerprint of high-density water. As a consequence, the analogy between the structure of high-density water and those of high-density ices is evidenced.
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New topochemistry in simple molecular systems can be explored at high pressure. Here we examine the binary nitrogen/hydrogen system using Raman spectroscopy, synchrotron X-ray diffraction, synchrotron infrared microspectroscopy and visual observation. We find a eutectic-type binary phase diagram with two stable high-pressure van der Waals compounds, which we identify as (N2)6(H2)7 and N2(H2)2. The former represents a new type of van der Waals host-guest compound in which hydrogen molecules are contained within channels in a nitrogen lattice. This compound shows evidence for a gradual, pressure-induced change in bonding from van der Waals to ionic interactions near 50 GPa, forming an amorphous dinitrogen network containing ionized ammonia in a room-temperature analogue of the Haber-Bosch process. Hydrazine is recovered on decompression. The nitrogen-hydrogen system demonstrates the potential for new pressure-driven chemistry in high-pressure structures and the promise of tailoring molecular interactions for materials synthesis.
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We report the first application of a multichannel collimator (MCC) to perform quantitative structure factor measurements of dense low-Z fluids in a diamond anvil cell (DAC) using synchrotron x-ray diffraction. The MCC design, initially developed for the Paris-Edinburgh large volume press geometry, has been modified for use with diamond anvil cells. A good selectivity of the diffracted signal of the dense fluid sample is obtained due to a large rejection of the Compton diffusion from the diamond anvils. The signal to background ratio is significantly improved. We modify previously developed analytical techniques for quantitative measurement of the structure factor of fluids in DACs [J. H. Eggert, G. Weck, P. Loubeyre, and M. Mezouar, Phys. Rev. B 65, 174105 (2002)] to account for the contribution of the MCC. We present experimental results on liquids argon and hydrogen at 296 K to validate our method and test its limits, respectively.
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We report the observation of a roughening transition in carbon dioxide along the melting line of phase I, which we call reverse as faceting appears with increasing temperature. The characteristics of the transition are discussed in light of modern theories of roughening and the causes of its reverse behavior investigated. We propose that high temperature faceting is related to a pressure-induced increase of the surface stiffness.
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The melting curve and fluid equation of state of carbon dioxide have been determined under high pressure in a resistively heated diamond anvil cell. The melting line was determined from room temperature up to 11.1+/-0.1 GPa and 800+/-5 K by visual observation of the solid-fluid equilibrium and in situ measurements of pressure and temperature. Raman spectroscopy was used to identify the solid phase in equilibrium with the melt, showing that solid I is the stable phase along the melting curve in the probed range. Interferometric and Brillouin scattering experiments were conducted to determine the refractive index and sound velocity of the fluid phase. A dispersion of the sound velocity between ultrasonic and Brillouin frequencies is evidenced and could be reproduced by postulating the presence of a thermal relaxation process. The Brillouin sound velocities were then transformed to thermodynamic values in order to calculate the equation of state of fluid CO2. An analytic formulation of the density with respect to pressure and temperature is proposed, suitable in the P-T range of 0.1-8 GPa and 300-700 K and accurate within 2%. Our results show that the fluid above 500 K is less compressible than predicted from various phenomenological models.
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This paper presents recent improvement on sound velocity measurements under extreme conditions, illustrated by the hypersonic sound velocity measurements of water up to 723 K and 9 GPa using Brillouin scattering technique. Because water at high pressure and high temperature is chemically very aggressive, these experiments have been carried out using a specific experimental set-up. The present data should be useful to better constrain the water equation of state at high density. This new development brings high-quality elastic data in a large pressure/temperature domain, which may afterwards benefit the understanding of many other fields as nonlinear acoustics, underwater sound, or physical acoustics from a more general point of view.