High-pressure Phase Transition Research Articles

High-Pressure Raman Study of n-Octane up to 15 GPa.

The high-pressure (HP) phase transition and conformational change of n-octane (hereafter abbreviation as n-C8) up to 15.3 GPa were studied using Raman spectroscopy to investigate the relationship between the HP phase state and the alkyl chain length of n-alkanes. The Raman spectral analysis of n-C8 indicated that the liquid-solid transition (solidification) occurs at ∼0.9 GPa and that the corresponding transition pressure of n-alkanes depends on their density. Further pressurization at ∼4 GPa increased the population of the gauche conformer, while the solid (order)-amorphous transition occurred at ∼6 GPa along with a change in the full width at half maximum of the ruby R1 fluorescence line. The comparison of our findings with previously reported results suggested that the even-odd effect in the HP phase transition after solidification of n-alkanes appears between n-C7 and n-C8 as their HP phase transition up to ∼15 GPa was different.

Modification of the spectroscopic properties of Tb2O3 phosphor under the high-pressure phase transitions sequence

The high-pressure behavior of cubic Tb2O3 phase (C-type) has been investigated by in situ photoluminescence and Raman spectroscopy up to 18 GPa and 22 GPa, respectively. The luminescence spectrum of Tb2O3 at ambient conditions shows its characteristic sharp-line emission bands with the most intense one corresponding to the 5D4 - 7F5 transition, responsible for the green emission. Excitation and emission spectra measured at low temperature and at different emission and excitation wavelengths suggest that photoluminescence is governed by the Tb3+ in the non-centrosymmetric site (C2). A phase transition between 7.2 and 8.6 GPa is observed by Raman and photoluminescence experiments and is associated with a cubic-to-monoclinic (B-type) structural transformation. From 14 GPa the predominant modes in the Raman spectrum correspond to those from the trigonal phase (A-type), indicating that the pressure-induced structural phase transition sequence of Tb2O3 is C → B → A. Upon pressure release, the starting cubic phase is not recovered, but the monoclinic one.

Equation of state and high-pressure phase behaviour of SrCO<sub>3</sub>

Abstract. The high-pressure phase transition of strontianite (SrCO3) was investigated at ambient temperature by means of powder and single-crystal X-ray diffraction. The samples were compressed in a diamond anvil cell to a maximum pressure of 49 GPa. Structure refinements confirm the existence of SrCO3 in the low pressure aragonite-type phase Pmcn (62) up to about 26 GPa. Above this pressure, SrCO3 transforms into a high-pressure phase with post-aragonite crystal structure Pmmn (59). Fitting the volume extracted from the compression data to the third-order Birch–Murnaghan equation of state for the low-pressure phase of SrCO3 yields K0=62.7(6) GPa and K0′=3.2(1), and for the high-pressure phase this yields K0=103(10) GPa and K0′=2.3(6). The unit cell parameters change non-uniformly, with the c axis being 4 times more compressible than the a and b axes. Our results unequivocally show the existence of a Pmmn structure in SrCO3 above 26 GPa and provide important structural parameters for this phase.

Discovery of terrestrial allabogdanite (Fe,Ni)2P, and the effect of Ni and Mo substitution on the barringerite-allabogdanite high-pressure transition

Abstract Minerals formed at high pressures are sensitive indicators of extreme pressure-temperature conditions that occur in nature. The discovery of the high-pressure polymorph of (Fe,Ni)2P, allabogdanite in the surficial pyrometamorphic rocks of the Hatrurim Formation (the Mottled Zone) surrounding the Dead Sea basin in Israel is the first terrestrial occurrence of a mineral previously only found in iron meteorites. Stepwise annealing experiments demonstrate that allabogdanite is metastable at ambient pressure and that it irreversibly transforms into its low-pressure polymorph, barringerite, upon heating to 850 ± 50 °C. High-pressure, high-temperature diamond-anvil cell (DAC) experiments confirm the results of annealing experiments. The DAC data indicate that Hatrurim allabogdanite is metastable below 7.4 GPa, and the low-to high-pressure phase transition (barringerite → allabogdanite) occurs at 25 ± 3 GPa and 1400 ± 100 °C. The observed transition pressure of Hatrurim allabogdanite is significantly higher than that of pure synthetic Fe2P (8 GPa) due to partial substitution of Fe for Ni (4 wt%) and Mo (2.5 wt%). Because the influence of substituting impurities on the conditions of phase transitions can be unexpectedly strong, our findings confirm that caution should be exercised when extrapolating data from experiments on synthetic compounds to natural systems. Based on the discovery of terrestrial allabogdanite (Fe,Ni)2P coupled with experiments probing the phase transitions in this natural composition, we contend that terrestrial allabogdanite formed via transformation from barringerite and posit potential scenarios of its formation.

Crystal Growth and Investigation of High-Pressure Physical Properties of Fe2As

We reported the growth of Fe2As single crystals and the study of its physical properties via comprehensive measurements, such as transport properties under pressure and high-pressure synchrotron radiation X-ray diffraction. Fe2As is an antiferromagnetic metal with TN ~ 355 K. Within the pressure range of 100 GPa, no superconductivity was observed above 2 K. The abrupt drop in resistance from 21 to 31.7 GPa suggests a high-pressure phase transition happens. The high-pressure X-ray experiments indicate a new high-pressure phase appears, starting from 27.13 GPa. After the refinement of the high-pressure X-ray data, the pressure dependence of lattice constants of Fe2As (P4/nmm phase) was plotted and the bulk modulus B0 was obtained to be 168.6 GPa.

High-pressure phase transition, elastic properties and lattice vibration modes in Rb2S compound material

The structural, electronic, elastic and lattice dynamics properties of the ground state and high-pressure phases, namely the antifluorite, anticotunnite and Ni2In-type structures ofdirubidium sulphideare reported using the pseudopotential plane wave method within the framework of density functional theory.The structural parameters are optimized within the usual accuracy range of such calculations. The electronic band structures, total and orbital decomposed densities of states(DOS) are analysed and discussed. The band gap of Rb2S changes from an indirect in the antifluorite structure to a direct in the anticotunnite and Ni2In-type structures. The valence states near the Fermi energy are dominated by S-p states, and there is no hybridization of the electronic valence bands in all the considered structures, which confirms the ionic character of the bonds.Evaluated elastic constants propose that the material of interest is mechanically stable in all studied structures.Besides, the examination of the phonon dispersion curves and their corresponding DOSsusing a linear response approach based on the density functional perturbation theory shows that the material in question is dynamically stable in the antifluorite and anticotunnite structures.

High-Pressure Behaviors of Ag2S Nanosheets: An in Situ High-Pressure X-Ray Diffraction Research.

An in situ high-pressure X-ray diffraction study was performed on Ag2S nanosheets, with an average lateral size of 29 nm and a relatively thin thickness. Based on the experimental data, we demonstrated that under high pressure, the samples experienced two different high-pressure structural phase transitions up to 29.4 GPa: from monoclinic P21/n structure (phase I, α-Ag2S) to orthorhombic P212121 structure (phase II) at 8.9 GPa and then to monoclinic P21/n structure (phase III) at 12.4 GPa. The critical phase transition pressures for phase II and phase III are approximately 2–3 GPa higher than that of 30 nm Ag2S nanoparticles and bulk materials. Additionally, phase III was stable up to the highest pressure of 29.4 GPa. Bulk moduli of Ag2S nanosheets were obtained as 73(6) GPa for phase I and 141(4) GPa for phase III, which indicate that the samples are more difficult to compress than their bulk counterparts and some other reported Ag2S nanoparticles. Further analysis suggested that the nanosize effect arising from the smaller thickness of Ag2S nanosheets restricts the relative position slip of the interlayer atoms during the compression, which leads to the enhancing of phase stabilities and the elevating of bulk moduli.

Weak Coulomb correlations stabilize the electride high-pressure phase of elemental calcium

Theoretical studies using the state-of-the-art density functional theory and dynamicalmean-field theory (DFT + DMFT) method show that weak electronic correlation effects are crucial for reproducing the experimentally observed pressure-induced phase transitions of calcium from β-tin to Cmmm and then to the simple cubic structure. The formation of an electride state in calcium leads to the emergence of partially filled and localized electronic states under compression. The electride state was described using a basis containing molecular orbitals centered on the interstitial site and Ca-d states. We investigate the influence of Coulomb correlations on the structural properties of elemental Ca, noting that approaches based on the Hartree–Fock method (DFT + U or hybrid functional schemes) are poorly suited for describing correlated metals. We find that only the DFT + DMFT method reproduces the correct sequence of high-pressure phase transitions of Ca at low temperatures.

High-pressure phase transition of methane hydrate in water–methane–ammonia system

The phase transition of methane hydrate in water–methane–ammonia system was investigated under pressures up to 20 GPa using synchrotron X-ray powder diffraction (XRD) combined with diamond anvil cells. The XRD experiments revealed that the sI cage structure (MH-I) of methane hydrate transforms into an sH cage structure (MH-II) at approximately 1 GPa, further transforms into a filled-ice Ih structure (MH-III) at approximately 2 GPa, and remains in this structure under pressures up to at least 20 GPa. Ammonia was observed as ammonia hemihydrate phase-II above 3.8 GPa. It is therefore considered that methane hydrate can coexist with aqueous ammonia below 3.8 GPa and coexist with ammonia hemihydrate phase-II above 3.8 GPa. The transition pressures of methane hydrate in the investigated system were consistent with those in water–methane system. These results indicate that, although ammonia is thought to inhibit methane hydrate formation, methane hydrate can be stable in water–methane–ammonia system up to at least 20 GPa and at room temperature. The pressure range in this study covered the pressure conditions inside icy moons, indicating that methane hydrate has a potential to be the main constituent of them.

Enhanced Thermoelectric Performances Driven by High-Pressure Phase Transition of Mg2Sn Compound

The ground state properties of the Mg2Sn compound under seven different crystal structures were studied using a first principles approach based on the full-potential augmented plane wave method FP-LAPW within the GGA-PBEsol approximation. We fixed the cubic structure of CaF2-type as zero pressure phase and we have considered the orthorhombic PbCl2-type, hexagonal Ni2In-type, tetragonal Al2Cu-type, cubic MgCu2-type, hexagonal MgZn2-type and dihexagonal MgNi2-type as candidates structures for the high-pressure phases. We used Gibbs’ equation to examine these high-pressure structures and compare their enthalpies. Thus, it appears that the Mg2Sn compound undergoes three pressure-induced phase transitions. First, it is a transition from the CaF2-type cubic structure to the orthorhombic PbCl2-type structure; second, the transition from the PbCl2-type structure to the hexagonal Ni2In-type structure; and third, the transition will take place toward the cubic structure MgCu2-type which should be stable. In addition, to further examine the thermoelectric performances of each stable phase, we combined the results calculated for the electronic properties by the TB-mBJ approximation with the semi-classical Boltzmann theory using the BoltzTraP code. Our key result is that Mg2Sn compound with cubic MgCu2-type structure has a high value of figure of merit (ZTe) compared to the cubic CaF2-type structure, which could promise it as an excellent candidate for potential thermoelectric applications at high pressure.

High-pressure silica phase transitions: Implications for deep mantle dynamics and silica crystallization in the protocore

AbstractThe subsolidus phase diagram of silica in the 80–220 GPa pressure range was determined by density functional theory (DFT). The transition pressures calculated using the generalized gradient approximation (GGA) in the static limit (at 0 K, without zero point vibrational energy) for the β-stishovite (CaCl2-structure) to seifertite and the seifertite to pyrite-type transitions are 95 and 213 GPa, respectively. These are in good agreement with those calculated using hybrid functionals, giving transition pressures of 96 and 215 GPa. This indicates that previous local density approximation (LDA) results underestimate the transition pressure by 10–15 GPa. Density functional perturbation theory calculations, carried out using GGA within the quasi-harmonic approximations, give Clapeyron slopes of 5.4 and −2.8 MPa/K for the β-stishovite to seifertite and seifertite to pyrite-type transitions, respectively. This suggests that the seifertite-forming transition occurs at 109 GPa (470 km above the core-mantle boundary, CMB) at an ambient mantle geotherm, whereas the pyrite-type transition occurs at 200 GPa (620 km below the CMB) at 4700 K, which is close to the core adiabat. We also calculate the equation of state and show that the stability of seifertite in the lowermost mantle contributes negative buoyancy to recycled oceanic crust, although not as much as in some previous studies. Nevertheless, the increased density of seifertite over β-stishovite may lead to layers with elevated proportions of basaltic material within the large low S-wave velocity provinces. The seifertite to pyrite-type silica transition in the outer core will affect the silica liquidus surface in the system Fe-Si-O and forms a basis for further investigations of silica crystallization in the protocore.

Pressure-Induced Topological and Structural Phase Transitions in an Antiferromagnetic Topological Insulator**Supported by the National Key Research and Development Program of China under Grant Nos. 2018YFA0704300 and 2017YFE0131300, the National Natural Science Foundation of China under Grant Nos. U1932217, 11974246, 11874263 and 10225417, and the Natural Science Foundation of Shanghai under Grant No. 19ZR1477300. The authors thank the support from Analytical

Recently, natural van der Waals heterostructures of (MnBi2Te4)m(Bi2Te3)n have been theoretically predicted and experimentally shown to host tunable magnetic properties and topologically nontrivial surface states. We systematically investigate both the structural and electronic responses of MnBi2Te4 and MnBi4Te7 to external pressure. In addition to the suppression of antiferromagnetic order, MnBi2Te4 is found to undergo a metal–semiconductor–metal transition upon compression. The resistivity of MnBi4Te7 changes dramatically under high pressure and a non-monotonic evolution of ρ (T) is observed. The nontrivial topology is proved to persist before the structural phase transition observed in the high-pressure regime. We find that the bulk and surface states respond differently to pressure, which is consistent with the non-monotonic change of the resistivity. Interestingly, a pressure-induced amorphous state is observed in MnBi2Te4, while two high-pressure phase transitions are revealed in MnBi4Te7. Our combined theoretical and experimental research establishes MnBi2Te4 and MnBi4Te7 as highly tunable magnetic topological insulators, in which phase transitions and new ground states emerge upon compression.

Effect of Extra-Framework Cations on Negative Linear Compressibility and High-Pressure Phase Transitions: A Study of KCd[Ag(CN)2]3.

The negative thermal expansion material potassium cadmium dicyanoargentate, KCd[Ag(CN)2]3, is studied at high pressure using a combination of X-ray single-crystal diffraction, X-ray powder diffraction, infrared and Raman spectroscopy, and density functional theory calculations. In common with the isostructural manganese analogue, KMn[Ag(CN)2]3, this material is shown to exhibit very strong negative linear compressibility (NLC) in the crystallographic c direction due to structure hinging. We find increased structural flexibility results in enhanced NLC and NTE properties, but this also leads to two pressure-induced phase transitions—to very large unit cells involving octahedral tilting and shearing of the structure—below 2 GPa. The presence of potassium cations has an important effect on the mechanical and thermodynamic properties of this family, while the chemical versatility demonstrated here is of considerable interest to tune unusual mechanical properties for application.

Universal Phase Transitions of AlB2-Type Transition-Metal Diborides.

High-pressure phase transitions of AlB2-type transition-metal diborides (TMB2; TM = Zr, Sc, Ti, Nb, and Y) were systematically investigated using first-principles calculations. Upon subjecting to pressure, these TMB2 compounds underwent universal phase transitions from an AlB2-type to a new high-pressure phase tP6 structure. The analysis of the atomistic mechanism suggests that the tP6 phases result from atomic layer folds of the AlB2-type parent phases under pressure. Stability studies indicate that the tP6-structured ZrB2, ScB2, and NbB2 are stable and may be observed under high pressure and the tP6-structured TiB2 phase may be recovered at ambient pressure.

Effect of Alkali and Trivalent Metal Ions on the High-Pressure Phase Transition of [C2H5NH3]MI 0.5MIII 0.5(HCOO)3 (MI = Na, K and MIII = Cr, Al) Heterometallic Perovskites.

We report the high-pressure behavior of two perovskite-like metal formate frameworks with the ethylammonium cation (EtAKCr and EtANaAl) and compare them to previously reported data for EtANaCr. High-pressure single-crystal X-ray diffraction and Raman data for EtAKCr show the occurrence of two high-pressure phase transitions observed at 0.75(16) and 2.4(2) GPa. The first phase transition involves strong compression and distortion of the KO6 subnetwork followed by rearrangement of the −CH2CH3 groups from the ethylammonium cations, while the second involves octahedral tilting to further reduce pore volume, accompanied by further configurational changes of the alkyl chains. Both transitions retain the ambient P21/n symmetry. We also correlate and discuss the influence of structural properties (distortion parameters, bulk modulus, tolerance factors, and compressibility) and parameters calculated by using density functional theory (vibrational entropy, site-projected phonon density of states, and hydrogen bonding energy) on the occurrence and properties of structural phase transitions observed in this class of metal formates.

Symmetry-Adapted Finite Strain Landau Theory Applied to KMnF3

In recent years, finite strain Landau theory has been gradually developed as both a conceptual as well as a quantitative framework to study high pressure phase transitions of the group-subgroup type. In the current paper, we introduce a new version of this approach which is based on symmetry-adapted finite strains. This results in a substantial simplification of the original formulation. Moreover, it allows for replacing the clumsy use of truncated Taylor expansions by a convenient functional parametrization. Both the weaknesses of the traditional Landau approach based on infinitesimal strains as well as the major improvements made possible by our new parametrization are illustrated in great detail in an application to the ambient temperature high pressure transition of the perovskite KMnF 3 .

A Short Review of Current Computational Concepts for High-Pressure Phase Transition Studies in Molecular Crystals

High-pressure chemistry of organic compounds is a hot topic of modern chemistry. In this work, basic computational concepts for high-pressure phase transition studies in molecular crystals are described, showing their advantages and disadvantages. The interconnection of experimental and computational methods is highlighted, showing the importance of energy calculations in this field. Based on our deep understanding of methods’ limitations, we suggested the most convenient scheme for the computational study of high-pressure crystal structure changes. Finally, challenges and possible ways for progress in high-pressure phase transitions research of organic compounds are briefly discussed.

High-Pressure Phase Transitions of Zinc Difluoride up to 55 GPa.

Studying the effect of high pressure (exceeding 10 kbar) on the structure of solids allows us to gain deeper insight into the mechanism governing crystal structure stability. Here, we report a study on the high-pressure behavior of zinc difluoride (ZnF2)-an archetypical ionic compound which at ambient pressure adopts the rutile (TiO2) structure. Previous investigations, limited to a pressure of 15 GPa, revealed that this compound undergoes two pressure-induced phase transitions, i.e., TiO2 → CaCl2 at 4.5 GPa and CaCl2 → HP-PdF2 at 10 GPa. Within this joint experimental-theoretical study, we extend the room-temperature phase diagram of ZnF2 up to 55 GPa. By means of Raman spectroscopy measurements we identify two new phase transitions, HP-PdF2 → HP1-AgF2 at 30 GPa and HP1-AgF2 → PbCl2 at 44 GPa. These results are confirmed by density functional theory calculations which indicate that in the HP1-AgF2 polymorph the coordination sphere of Zn2+ undergoes drastic changes upon compression. Our results point to important differences in the high-pressure behavior of ZnF2 and MgF2, despite the fact that both compounds contain cations of similar size. We also argue that the HP1-AgF2 structure, previously observed only for AgF2, might be observed at large compression in other AB2 compounds.

Judging the phase transition pressure of the unknown parent phase if the resulting state is known.

In high-pressure phase transition experiments, the crystal structure of the intermediate phase in some phase transitions is difficult to successfully measure due to the limitations of the experimental conditions. The absence of crystal structure data for the intermediate phase also makes it difficult to calculate the pressure point from the intermediate phase to the new phase by the traditional thermodynamic criterion in theoretical simulations. The Conch Criterion is employed by us to successfully verify the phase transition points by observing the reverse shifts of the DOS (electron density of states) curves for the new phase of Cu2S, PbS, PbSe and PbTe, which breaks through the constraints of the traditional criterion and realizes tracing the source of the phase transition in theoretical calculations.

High pressure phase transitions and physical properties of Li2MgH4; implications for hydrogen storage

A systematic calculation has been performed in order to study phase transitions and hydrogen storage properties of ternary hydride Li2MgH4 under pressure. The structural, elastic, electronic and vibrational properties of Li2MgH4 are collected by means of density functional theory. There are three phases identified; Pbam at 0 GPa,Pnma at 5 GPa and Pna21 at 65 GPa Pbam and Pnma phases of Li2MgH4 are found to be mechanically and dynamically stable. Ductility of the phases are determined based on Pugh's criteria. It is found that Li2MgH4 becomes ductile at 5 GPa, otherwise it is a brittle material. Electronic band structures and corresponding partial density of states of phases are also obtained. All phases at 0 GPa, 5 GPa and 65 GPa have wide band gaps, indicating that Li2MgH4 is an insulator at all pressures. The phonon dispersion curves of Pbam and Pnma phases have no imaginary frequency indicating that both phases of Li2MgH4 are dynamically stable. The gravimetric hydrogen density of Li2MgH4 is calculated as 10.52 wt %, which is a great rate along with the hydrogen desorption temperature of 670 K.