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We have examined the effect of composition on the Raman-active vibrational response of the Cu2(Fe x Zn1−x )SnS4 and Cu2(Mn x Zn1−x )SnS4 solid solution series at ambient conditions. Based on these results we were able to identify the phase boundaries of the respective kesterite-type and stannite-type structures adopted by these compounds as a function of composition. In the case of Cu2(Fe x Zn1−x )SnS4, our observations correlate very well with earlier reports. For the Cu2(Mn x Zn1−x )SnS4 series, on the other hand, we were able to clearly pinpoint the kesterite↔stannite transition for intermediate compositions for the first time, indicating that Raman spectroscopy can serve as an efficient method for monitoring subtle structural transitions in these systems.

We have studied the high-pressure vibrational and structural behavior of bulk graphite and graphene nanoplatelets at room temperature by means of high-pressure Raman spectroscopic and x-ray diffraction probes. We have detected a clear pressure-induced structural transition in both materials, evidenced by the appearance of new Bragg peaks and Raman features, deviating from the starting hexagonal graphitic structure. The high-pressure phase is identified as a partially disordered orthorhombic structure, consisting of mixed sp2- and sp3-type bonding. Our experimental findings serve as direct evidence for the existence of a metastable transient modification in cold compressed carbon, lying between the sp2-type graphite and sp3-type diamond allotropes.

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 K 0 ′ = 3.2 ( 1 ) , and for the high-pressure phase this yields K0=103(10) GPa and K 0 ′ = 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.

The high-pressure CaCO3 phase diagram has been the most extensively studied within the carbonates group. However, both the diverse mineralogy of carbonates and the abundance of solid solutions in natural samples require the investigation of multi-component systems at high pressures (P) and temperatures (T). Here we studied a member of the CaCO3–SrCO3 solid-solution series and revealed the effect of cationic substitution on the pressure-induced phase transitions in calcium carbonate. A synthetic solid solution Ca0.82Sr0.18CO3 was studied in situ by Raman spectroscopy in a diamond-anvil cell (DAC) up to 55 GPa and 800 K. The results of this work show significant differences in the high-pressure structural and vibrational behavior of the (Ca,Sr)CO3 solid solution compared to that of pure CaCO3. The monoclinic CaCO3-II-type structure (Sr-calcite-II) was observed already at ambient conditions instead of the “expected” rhombohedral calcite. The stress-induced phase transition to a new high-pressure modification, termed here as Sr-calcite-IIIc, was detected at 7 GPa. Sr-calcite-VII formed already at 16 GPa and room T, which is 14 GPa lower compared to CaCO3-VII. Finally, crystallization of Sr-aragonite was detected at 540 K and 9 GPa, at 200 K lower T than pure aragonite. Our results indicate that substitution of Ca2+ by bigger cations, such as Sr2+, in CaCO3 structures can stabilize phases with larger cation coordination sites (e.g., aragonite, CaCO3-VII, and post-aragonite) at lower P-T conditions compared to pure CaCO3. The present study shows that the role of cationic composition in the phase behavior of carbonates at high pressures should be carefully considered when modeling the deep carbon cycle and mantle processes involving carbonates, such as metasomatism, deep mantle melting, and diamond formation.

High-pressure and high-temperature Raman spectra of synthetic FeCO 3 siderite and Mg 0.76 Fe 0.24 CO 3 magnesite were measured across the spin transition up to nearly 60 GPa and 700 K. In pure siderite the spin transition is sharp and observed between 44 and 46 GPa, with no discernible temperature dependence up to 700 K. The spin transition in Fe-bearing magnesite (“ferromagnesite”) is also sharp and takes place between 45 and 47 GPa at ambient temperature, whereas the transition pressure range broadens significantly at about 600 K (45–52 GPa). Our results suggest that the onset pressure of the spin transition in the siderite–magnesite solid solution series is independent of temperature and composition up to 700 K, whereas the broadening of the spin transition range at higher temperature is driven by the Mg content of the sample. Finally, comparison of the (Mg,Fe)CO 3 and the (Mg,Fe)O systems indicates that the onset pressure of the spin transition is temperature-independent in both cases, which is rationalized in terms of the FeO 6 octahedral compression.

An alkali niobate-silicate veneer ceramic for ZrO2-based dental restoration was developed and characterized for its physical properties and structure. The properties were adjusted for dental applications. The new lithium disilicate glass-ceramic VBK (sold as cerafusion or LiSi) can easily be applied by spray coating to any individually formed ZrO2-matrix and needs only one final tempering treatment. The surface of the glass-ceramic is very smooth. The color of the already translucent glass-ceramic can be adjusted to that of individual natural teeth. The structure of the glass-ceramicwas studied by XRD and Ramanspectroscopy as a function of heat-treatment and of spatial variations within the material and at its interfaces. ToF SIMS, SEM and thermal analysis techniques were applied to investigate the crystallization behavior and surface-interface reactions. XRD and Raman spectroscopy identified different crystalline phases in the amorphous glass matrix including Li2Si2O5, Li2SiO3, NaxLi(1−x)NbO3 and Na3NbO4. The Raman spectrum of the amorphous matrix is dominated by the vibrational activity of the highly polarizable niobate units with a prominent feature at 865 cm−1, assigned to Nb-O stretching in NbO6 octahedra, which have non-bridging oxygen atoms and are connected to the silicate matrix rather than to other niobate polyhedra.

We have examined the effect of temperature and pressure on the Raman-active G-band of graphene nanoplatelets with an average thickness of 4 nm. Measuring the Raman mode frequency and width of the G-band as a function of temperature and pressure allowed us to extract the individual factors contributing to the frequency and width of the G-band, that is, the volumetric (thermal expansion) and anharmonic (phonon–phonon interactions) terms responsible for the Raman shift and the electron–phonon coupling and anharmonic contributions controlling the width/lifetime of the G-band. Considering the available literature, the significant role of the anharmonic effects in understanding the G-band physical processes in carbon-based systems is highlighted.

Using optical absorption and Raman spectroscopic measurements, in conjunction with the first-principles calculations, a pressure-induced high-spin (HS)-to-low-spin (LS) state electronic transition of Fe2+ (M2-octahedral site) was resolved around 76-80GPa in a natural triphylite-lithiophilite sample with chemical composition (LiFe0.7082+Mn0.292PO4)-Li-M1-Fe-M2 (theoretical composition (LiFe0.52+Mn0.5PO4)-Li-M1-Fe-M2). The optical absorption spectra at ambient conditions consist of a broad doublet band with two constituents (1) (similar to 9330cm(-1)) and (2) (similar to 7110cm(-1)), resulting from the electronic spin-allowed transition (T2gEg)-T-5-E-5 of octahedral (HSFe2+)-Fe-M2. Both (1) and (2) bands shift non-linearly with pressure to higher energies up to similar to 55GPa. In the optical absorption spectrum measured at similar to 81GPa, the aforementioned HS-related bands disappear, whereas a new broadband with an intensity maximum close to 16,360cm(-1) appears, superimposed on the tail of the high-energy ligand-to-metal O2-Fe2+ charge-transfer absorption edge. We assign this new band to the electronic spin-allowed dd-transition (1)A(1g)(1)T(1g) of LS Fe2+ in octahedral coordination. The high-pressure Raman spectra evidence the Fe2+ HS-to-LS transition mainly from the abrupt shift of the P-O symmetric stretching modes to lower frequencies at similar to 76GPa, the highest pressure achieved in the Raman spectroscopic experiments. Calculations indicated that the presence of Mn-M2(2+) simply shifts the isostructural HS-to-LS transition to higher pressures compared to the triphylite Fe-M2(2+) end-member, in qualitative agreement with our experimental observations.

High-pressure molybdenum dioxide (HP-MoO2) was synthesized using a multianvil press at 18 GPa and 1073 K, as motivated by previous first-principles calculations. The crystal structure was determined by single-crystal X-ray diffraction. The new polymorph crystallizes isotypically to HP-WO2 in the orthorhombic crystal system in space group Pnma and was found to be diamagnetic. Theoretical investigations using structure optimization at density-functional theory (DFT) level indicate a transition pressure of 5 GPa at 0 K and identify the new compound as slightly metastable at ambient pressure with respect to the thermodynamically stable monoclinic MoO2 (α-MoO2; ΔEm = 2.2 kJ·mol–1).

We have conducted high pressure far-infrared absorbance and Raman spectroscopic investigations on a natural iron-free dolomite sample up to 40 GPa. Comparison between the present observations and literature results unraveled the effect of hydrostatic conditions on the high pressure dolomite polymorph adopted close to 40 GPa, i.e. the triclinic Dol-IIIc modification. In particular, non-hydrostatic conditions impose structural disorder at these pressures, whereas hydrostatic conditions allow the detection of an ordered Dol-IIIc vibrational response. Hence, hydrostatic conditions appear to be a key ingredient for modeling carbon subduction at lower mantle conditions. Our complementary first-principles calculations verified the far-infrared vibrational response of the ambient- and high pressure dolomite phases.

Our joint high-pressure and high-temperature mid-infrared absorbance and Raman investigations on a synthetic strontianite sample led to the construction of the respective pressure–temperature P–T phase diagram (maximum P = 38 GPa, maximum T = 800 K). Our results allowed for the determination of the P–T slope for the onset pressure of the aragonite Pmcn → post-aragonite Pmmn structural transition reported in the literature, which is found to be negative and equal to ΔP/ΔT = − 0.012 GPa/K. The determined SrCO3 P–T phase diagram appears consistent with the respective P–T phase diagrams of relevant aragonite-type carbonates. In addition, we provide the first ever measured far-infrared absorbance spectra under pressure for the family of aragonite-type carbonates. Our complementary first-principle calculations were able to reproduce the infrared spectra of both Pmcn and Pmmn phases of strontianite.

Samples of the Cu2Cd x Zn1−x SnS4 solid solution series were synthesized by a mechanochemical process, exhibiting high crystallinity due to an annealing step under flowing H2S gas. The composition-dependent structural transition between the kesterite- and stannite-type phases was determined for Cd content close to x Cd ≈ 0.4 by means of x-ray diffraction and Raman spectroscopic probes, in excellent agreement with earlier investigations. Our DFT calculations predicted a critical Cd concentration value of x Cd = 0.5 as the 'border' between the stannite- and kesterite-type structure in the Cu2Cd x Zn1−x SnS4 solid solution series. The somewhat higher calculated Cd content value compared to the experimental case can be accounted by partial Cu/Zn disorder present in the synthesized samples. The measured optical band gaps E g of the Cu2Cd x Zn1−x SnS4 solid solution series decrease by ~0.3 eV upon immediate introduction of Cd into the lattice, with E g being almost constant with varying Cd concentration. All of our observations are interpreted within the framework of earlier reports on composition-dependent kesterite-to-stannite transition, where local structural variations due to the Zn2+ substitution by the larger Cd2+ cations appear to dictate the transition process.

We have conducted a comprehensive investigation of the optical and vibrational properties of the binary semiconductor SnSe as a function of temperature and pressure by means of experimental and ab initio probes. Our high-temperature investigations at ambient pressure have successfully reproduced the progressive enhancement of the free carrier concentration upon approaching the Pnma → Bbmm transition, whereas the pressure-induced Pnma → Bbmm transformation at ambient temperature, accompanied by an electronic semiconductor → semi-metal transition, has been identified for bulk SnSe close to 10 GPa. Modeling of the Raman-active vibrations revealed that three-phonon anharmonic processes dominate the temperature-induced mode frequency evolution. In addition, SnSe was found to exhibit a pressure-induced enhancement of the Born effective charge. Such behavior is quite unique and cannot be rationalized within the proposed effective charge trends of binary materials under pressure.

Bentonite was chemically pretreated with Ca(OH)2 to enhance orthophosphate phosphorus (OPP) sorption capacity (qe). The pretreatment resulted in an increase of qe from about 0.3 mg P per g to about 8 mg P per g at pH 7 and 25 °C, and of OPP concentration 100 mg P per L. The effects of solution pH, OPP concentration, sorbent dosage, and temperature on OPP sorption onto pretreated bentonite were investigated. The variation of initial pH (4–9) did not affect qe, however, re-adjustment of the final pH showed that the variation of the final pH had a significant positive effect on qe. The sorption kinetics showed a low rate, reaching half of qe in the first 4 h and equilibrium after 96 h. The calculated Langmuir qmax was 11.68 mg P per g. Thermodynamic analysis suggests that the sorption process is spontaneous and endothermic. Desorption of OPP was high in solutions of 0.1 M HCl and 0.01 EDTA-Na2 and reached 83% and 98%, respectively. We conclude that the predominant sorption mechanism for OPP uptake is inner-sphere surface complexation (ligand exchange). Other less important mechanisms such as surface precipitation and replacement of P5+ for Si4+ on the tetrahedral sites of montmorillonite may operate during the OPP uptake process by pretreated bentonite with Ca(OH)2.

Single crystals of the methylammonium MA lead halides MAPbI3, MAPbBr3, and MAPbCl3 have been investigated using infrared spectroscopy with the aim of analyzing structural and dynamical aspects of processes that enable the ordering of the MA molecule in the orthorhombic crystal structure of these hybrid perovskites. Our temperature dependent studies were focused on the analysis of the CH NH rocking, C N stretching, and CH NH bending modes of the MA molecule in the 800 1750 cm 1 frequency range. They deliver a direct comparison of the behaviors of the three halides on crossing the orthorhombic tetragonal phase transition in MA lead halide single crystals. Drastic changes of all vibrational modes close to the phase transition were clearly observed. Additional spectral features that were not discussed previously are pointed out. The transformation of the two dimensional orthorhombic hydrogen bond layers into a more three dimensional arrangement in the tetragonal phase seems to be an important feature providing deeper insights into the mechanisms that lead to a free rotating MA molecule in the inorganic host structure. The change of the molecule site symmetry in the tetragonal crystal structure seems to be an important feature of the orthorhombic tetragonal phase transition. For low temperatures, it can be stated that the iodide is stronger influenced by hydrogen bonding than the bromide and the chloride

Very recently an ultralow thermal conductivity and a surpassing high thermoelectric figure of merit were reported in SnSe which makes this material very attractive for electrical energy harvesting. In this paper we follow the evolution of the low-energy phonons with doping, temperature and pressure and compare the experimental results with ab initio calculations to help understanding better the low thermal conductivity in SnSe and may help developing highly efficient thermoelectric materials.

Physical review / B 97(18), 184405 (2018). doi:10.1103/PhysRevB.97.184405, We present a combination of first-principles and experimental results regarding the structural and magnetic properties of olivine-type $\mathrm{LiFePO_{4}}$ under pressure. Our investigations indicate that the starting $Pbnm$ phase of $\mathrm{LiFePO_{4}}$ persists up to 70 GPa. Further compression leads to an isostructural transition in the pressure range of 70–75 GPa, inconsistent with a former theoretical study. Considering our first-principles prediction for a high-spin to low-spin transition of $\mathrm{Fe^{2+}}$ close to 72 GPa, we attribute the experimentally observed isostructural transition to a change in the spin state of $\mathrm{Fe^{2+}}$ in $\mathrm{LiFePO_{4}}$. Compared to relevant Fe-bearing minerals, $\mathrm{LiFePO_{4}}$ exhibits the largest onset pressure for a pressure-induced spin state transition., Published by APS, Woodbury, NY

Iron oxide nanoparticles were prepared using the simplest and most efficient chemical route, the coprecipitation, in the absence and the presence of three different and widely used surfactants. The purpose of this study is to investigate the possible influence of the different surfactants on the structure and therefore on the magnetic properties of the iron oxide nanoparticles. Thus, different techniques were employed in order to elucidate the composition and structure of the magnetic iron oxide nanoparticles. By combining transmission electron microscopy with X-ray powder diffraction and X-ray absorption fine structure measurements, we were able to determine and confirm the crystal structure of the constituent iron oxides. The magnetic properties were investigated by measuring the hysteresis loops where the surfactant influence on their collective magnetic behavior and subsequent AC magnetic hyperthermia response is apparent. The results indicate that the produced iron oxide nanoparticles may be considered as good candidates for biomedical applications in hyperthermia treatments because of their high heating capacity exhibited under an alternating magnetic field, which is sufficient to provoke damage to the cancer cells.

High-pressure molybdenum dioxide (HP-MoO

A combined high-pressure mid-infrared absorption and Raman spectroscopy study on a natural CaMg0.98Fe0.02(CO3)2 dolomite sample was performed both at ambient and high temperatures. A pressure–temperature phase diagram was constructed for all the reported dolomite ambient- and high-pressure polymorphs. In addition, a local distortion of the ambient-pressure dolomite structure was identified close to 11 GPa, just before the transition toward the first known high-pressure phase. All the Clausius–Clapeyron slopes are found to be positive with similar magnitudes. Complementary first-principles calculations suggest a metastable nature of the high-pressure dolomite polymorphs. Finally, theoretical spectroscopy is used to interpret and discuss the observed changes in the measured vibrational spectra.

We have conducted high-pressure measurements on the CuCr2O4 and CuCr2Se4 spinels to unravel the structural systematics of these materials under compression. Our studies have revealed diverse structural behavior in these two compounds. In particular, CuCr2O4 retains its ambient-pressure I41/amd structure up to 50 GPa. Close inspection of the lattice and interatomic parameters reveals a compressibility change near 23 GPa, which is accompanied by an expansion of the apical Cr–O bond distances. We speculate that an outer Cr3+ 3d orbital reorientation might be at play in this system, manifesting as the change in compressibility at that pressure point. On the other hand, CuCr2Se4 undergoes a structural transformation from the starting Fd3m phase toward a monoclinic structure initiated at ∼8 GPa and completed at ∼20 GPa. This high-pressure behavior resembles that of ZnCr2Se4, and it appears that, unlike similar chalcogenide Cr spinels, steric effects take a leading role in this pressure-induced Fd3m → monoclin...

Applied physics letters 110(4), 041905 (2017). doi:10.1063/1.4974941, We have investigated the high-pressure structural and vibrational behavior of the ordered kesterite-type Cu$_{2}$ZnSnS$_{4}$ compound. Our investigations have revealed two structural transitions: a kesterite-to-disordered kesterite transition was observed between 7 and 9 GPa, which involves a Zn/Cu disorder within the respective cationic sublattice, whereas a rocksalt-type structure was realized at ∼15 GPa. The latter transition is accompanied by a cationic coordination increase from fourfold-to-sixfold with respect to the sulfur anions. The predicted kesterite-to-stannite transition was not detected. Furthermore, our high-pressure Raman studies have shown that the aforementioned Zn/Cu cationic disorder will always be present in Cu$_{2}$ZnSnS$_{4}$ under relatively moderate compression., Published by AIP Publishing , Melville, NY

The series of Cr-chalcogenide spinels ACr2X4 (A = Zn, Cd, Hg; X = S, Se) exhibits a rich phase diagram upon compression, as revealed by our recent investigations. There exist, however, some open questions regarding the role of cations in the observed structural transitions. In order to address these queries, we have performed X-ray diffraction and Raman spectroscopic studies on the ZnCr2S4 spinel up to 42 GPa, chosen mainly due to the similarity of the Zn2+ and Cr3+ cationic radii. Two reversible structural transitions were identified at 22 and 33 GPa, into a I41/amd and an orthorhombic phase, respectively. Close comparison with the behavior of relevant Cr-spinels revealed that the structural transitions are mainly governed by the competition of the magnetic exchange interactions present in these systems, and not by steric effects. In addition, careful inspection of the starting Fd3m phase revealed a previously unnoticed isostructural transition. The latter is intimately related to changes in the electro...

We have conducted high-pressure x-ray diffraction and Raman spectroscopic studies on the $\mathrm{CdC}{\mathrm{r}}_{2}\mathrm{S}{\mathrm{e}}_{4}$ spinel at room temperature up to 42 GPa. We have resolved three structural transitions up to 42 GPa, i.e., the starting $Fd\overline{3}m$ phase transforms at $\ensuremath{\sim}11\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$ into a tetragonal $I{4}_{1}/amd$ structure, an orthorhombic distortion was observed at $\ensuremath{\sim}15\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$, whereas structural disorder initiates beyond 25 GPa. Our ab initio density functional theory studies successfully reproduced the observed crystalline-to-crystalline structural transitions. In addition, our calculations propose an antiferromagnetic ordering as a potential magnetic ground state for the high-pressure tetragonal and orthorhombic modifications, compared with the starting ferromagnetic phase. Furthermore, the computational results indicate that all phases remain insulating in their stability pressure range, with a direct-to-indirect band gap transition for the $Fd\overline{3}m$ phase taking place at 5 GPa. We attempted also to offer an explanation behind the peculiar first-order character of the $Fd\overline{3}m(\mathrm{cubic})\ensuremath{\rightarrow}I{4}_{1}/amd$ (tetragonal) transition observed for several relevant Cr spinels, i.e., the sizeable volume change at the transition point, which is not expected from space group symmetry considerations. We detected a clear correlation between the cubic-tetragonal transition pressures and the next-nearest-neighbor magnetic exchange interactions for the Cr-bearing sulfide and selenide members, a strong indication that the cubic-tetragonal transitions in these systems are principally governed by magnetic effects.

Τhe magnetoelectric $\mathrm{ZnC}{\mathrm{r}}_{2}\mathrm{S}{\mathrm{e}}_{4}$ spinel, with space group $Fd\overline{3}m$, undergoes a reversible first-order structural transition initiating at 17 GPa, as revealed by our high-pressure x-ray diffraction studies at room temperature. We tentatively assign the high-pressure modification to an $A\mathrm{M}{\mathrm{o}}_{2}{\mathrm{S}}_{4}$-type phase, a distorted variant of the monoclinic $\mathrm{C}{\mathrm{r}}_{3}{\mathrm{S}}_{4}$ structure. Furthermore, our Raman investigation provides evidence for a pressure-induced insulator-metal transition. Our density functional theory calculations successfully reproduce the structural transition. They indicate significant band gap and magnetic moment reduction accompanying the pressure-induced structural modification. We discuss our findings in conjunction with the available high-pressure results on other Cr-based chalcogenide spinels.

Journal of applied physics 124(8), 085905 (2018). doi:10.1063/1.5047842, We have performed structural investigations of ordered kesterite-type Cu$_2$ZnSnS$_4$ up to 30 GPa. Our current X-ray diffraction results clearly excluded the presence of a kesterite → disordered kesterite transition reported previously between 7 and 9 GPa. Nevertheless, specific anomalies connected with the Cu-S bond length of the starting kesterite-type phase are evidenced close to 6 GPa, indicating subtle structural effects at play in this system. Moreover, we have indexed the high-pressure modification of Cu$_2$ZnSnS$_4$ adopted above 16 GPa to a disordered GeSb-type structure, a tetragonally distorted rocksalt-type modification. Full decompression leads to the adoption of a disordered sphalerite/zincblende-type structure. Our complementary density functional theory calculations reproduce accurately the experimental observations and indicate the possibility of a metallic high-pressure GeSb-type phase, unlike the starting semiconducting kesterite-type Cu$_2$ZnSnS$_4$structure., Published by American Inst. of Physics, Melville, NY

High-pressure Raman spectroscopy and x-ray diffraction of Sb2S3 up to 53 GPa reveals two phase transitions at 5 GPa and 15 GPa. The first transition is evidenced by noticeable compressibility changes in distinct Raman-active modes, in the lattice parameter axial ratios, the unit cell volume, as well as in specific interatomic bond lengths and bond angles. By taking into account relevant results from the literature, we assign these effects to a second-order isostructural transition arising from an electronic topological transition in Sb2S3 near 5 GPa. Close comparison between Sb2S3 and Sb2Se3 up to 10 GPa reveals a slightly diverse structural behavior for these two compounds after the isostructural transition pressure. This structural diversity appears to account for the different pressure-induced electronic behavior of Sb2S3 and Sb2Se3 up to 10 GPa, i.e. the absence of an insulator-metal transition in Sb2S3 up to that pressure. Finally, the second high-pressure modification appearing above 15 GPa appears to trigger a structural disorder at ~20 GPa; full decompression from 53 GPa leads to the recovery of an amorphous state.

The high-pressure structural and vibrational properties of Bi2S3 have been probed up to 65 GPa with a combination of experimental and theoretical methods. The ambient-pressure Pnma structure is found to persist up to 50 GPa; further compression leads to structural disorder. Closer inspection of our structural and Raman spectroscopic results reveals notable compressibility changes in specific structural parameters of the Pnma phase beyond 4-6 GPa. By taking the available literature into account, we speculate that a second-order isostructural transition is realized near that pressure, originating probably from a topological modification of the Bi2S3 electronic structure near that pressure. Finally, the Bi(3+) lone-electron pair (LEP) stereochemical activity decreases against pressure increase; an utter vanishing, however, is not expected until 1 Mbar. This persistence of the Bi(3+) LEP activity in Bi2S3 can explain the absence of any structural transitions toward higher crystalline symmetries in the investigated pressure range.

The cubic HgCr2Se4 spinel undergoes two structural transitions upon pressure increase. Initially, the ambient-pressure Fd-3m phase transforms into a tetragonal I41/amd structure above 15 GPa. We speculate that this Fd-3m-I41/amd transition is accompanied by an insulator-to-metal transition, resulting in the vanishing of the Raman signal after the structural transformation. Further compression of HgCr2Se4 leads to structural disorder beyond 21 GPa. Our spin-resolved band structure calculations reveal significant changes in the electronic structure of HgCr2Se4 after the Fd-3m-I41/amd transition, whereas the ferromagnetic interactions are found to dominate in both structures.

Selected members of the A2B3 (A = Sb, Bi; B = Se, Te) family are topological insulators. The Sb2Se3 compound does not exhibit any topological properties at ambient conditions; a recent high-pressure study, however, indicated that pressure transforms Sb2Se3 from a band insulator into a topological insulator above ~2 GPa; in addition, three structural transitions were proposed to occur up to 25 GPa. Partly motivated by these results, we have performed x-ray diffraction and Raman spectroscopy investigations on Sb2Se3 under pressure up to 65 GPa. We have identified only one reversible structural transition: the initial Pnma structure transforms into a disordered cubic bcc alloy above 51 GPa. On the other hand, our high-pressure Raman study did not reproduce the previous results; we attribute the discrepancies to the effects of the different pressure transmitting media used in the high-pressure experiments. We discuss the structural behavior of Sb2Se3 within the A2B3 (A = Sb, Bi; B = Se, Te) series.

Selected members of the A2B3 (A = Sb, Bi; B = Se, Te) family are topological insulators. The Sb2Se3 compound does not exhibit any topological properties at ambient conditions; a recent high-pressure study, however, indicated that pressure transforms Sb2Se3 from a band insulator into a topological insulator above ~2 GPa; in addition, three structural transitions were proposed to occur up to 25 GPa. Partly motivated by these results, we have performed x-ray diffraction and Raman spectroscopy investigations on Sb2Se3 under pressure up to 65 GPa. We have identified only one reversible structural transition: the initial Pnma structure transforms into a disordered cubic bcc alloy above 51 GPa. On the other hand, our high-pressure Raman study did not reproduce the previous results; we attribute the discrepancies to the effects of the different pressure transmitting media used in the high-pressure experiments. We discuss the structural behavior of Sb2Se3 within the A2B3 (A = Sb, Bi; B = Se, Te) series.

We have performed combined experimental and theoretical high-pressure investigations on magnetoelectric HgCr2S4 spinel. Overall, HgCr2S4 exhibits three reversible structural transitions under pressure: the starting Fd-3m phase adopts a tetragonal I41/amd structure at 20 GPa, an orthorhombic distortion occurs above 26 GPa, whereas a third structural transition takes place beyond 37 GPa. During the Fd-3m to I41/amd structural transition, HgCr2S4 experiences a volume change of 4% which is unexpected from space group symmetry considerations alone. Furthermore, the Fd-3m to I41/amd transformation appears to be concomitant with an insulator-to-metal transition whereas compression of HgCr2S4 leads to a gradual suppression of its ferromagnetism.