A MHz X-ray diffraction set-up for dynamic compression experiments in the diamond anvil cell.

An experimental platform for dynamic diamond anvil cell (dDAC) research has been developed at the High Energy Density (HED) Instrument at the European X-ray Free Electron Laser (European XFEL). Advantage was taken of the high repetition rate of the European XFEL (up to 4.5 MHz) to collect pulse-resolved MHz X-ray diffraction data from samples as they are dynamically compressed at intermediate strain rates (≤10 s), where up to 352 diffraction images can be collected from a single pulse train.

Evidence for superionic HO and diffusive He-HO at high temperature and high pressure.

We present the evidence of superionic phase formed in HO and, for the first time, diffusive HO-He phase, based on time-resolved x-ray diffraction experiments performed on ramp-laser-heated samples in diamond anvil cells. The diffraction results signify a similar bcc-like structure of superionic HO and diffusive He-HO, while following different transition dynamics. Based on time and temperature evolution of the lattice parameter, the superionic HO phase forms gradually in pure HO over the temperature range of 1350-1400 K at 23 GPa, but the diffusive He-HO phase forms abruptly at 1300 K at 26 GPa.

Crystal Structure of Symmetric Ice X in HO-H and HO-He under Pressure.

Ice VII and ice X are the two most dominant phases, stable over a large pressure range between 2 and 150 GPa and made of fundamentally different chemical bonding. Yet, the two ice phases share a similar bcc-based crystal structure and lattice constants, resulting in a challenge to discern the crystal structure of ice VII and ice X. Here, we present well-resolved X-ray diffraction data of HO in quasi-hydrostatic H and He pressure media, clearly resolving the two ice phases to 130 GPa and the dissociative nature of ice VII to X transition occurring at 20-50 GPa in HO-H and 60-70 GPa in HO-He.

X-ray Free Electron Laser-Induced Synthesis of ε-Iron Nitride at High Pressures.

The ultrafast synthesis of ε-FeN in a diamond-anvil cell (DAC) from Fe and N under pressure was observed using serial exposures of an X-ray free electron laser (XFEL). When the sample at 5 GPa was irradiated by a pulse train separated by 443 ns, the estimated sample temperature at the delay time was above 1400 K, confirmed by transformation of α- to γ-iron. Ultimately, the Fe and N reacted uniformly throughout the beam path to form FeN, as deduced from its established equation of state (EOS).

Transformation of molecular CO-III in low-density carbon to extended CO-V in porous diamond at high pressures and temperatures.

The ability to modify chemical bonding in dense heterogeneous solid mixtures by applying high pressure and temperature opens new opportunities to develop a greater number of novel materials with controlled structure, stability and exceptional physical properties. Here, we present the transformation of highly strained CO-III (Cmca) filled in porous low-density carbons (LDC) to extended CO-V (I-42d) encapsulated in porous diamond (Fd-3m) at high pressures and temperatures. The x-ray diffraction data indicates the density of porous diamond is about 5%-8% lower than that of bulk diamond and undergoes the structural distortion to monoclinic diamond (C2/m or M-carbon) upon pressure unloading.

Phase Diagram of Dense H_{2}-He Mixtures: Evidence for Strong Chemical Association, Miscibility, and Structural Change.

The phase diagram of hydrogen-helium mixtures is presented to 75 GPa, underscoring the formation of metastable H_{2}-rich crystallite in He-rich fluid mixtures and the structural phase transition in He lattice at ∼52  GPa. The Raman data also indicate a significant level of mixing between H_{2} and He even in solids, giving rise to new vibrational bands in He-rich solid at ∼2400  cm^{-1} for H-He stretching and 140  cm^{-1} for the lattice phonon of H_{2} incorporated hcp He. Therefore, the present result signifies unexpected, strong chemical association of the interstitial-filled guest molecules (H_{2} or He) with the host lattice (hcp He or H_{2}) in this quantum solid mixture.

Transformation of hydrazinium azide to molecular N at 40 GPa.

Hydrazinium azide (HA) has been investigated at high pressures to 68 GPa using confocal micro-Raman spectroscopy and synchrotron powder x-ray diffraction. The results show that HA undergoes structural phase transitions from solid HA-I to HA-II at 13 GPa, associated with the strengthening of hydrogen bonding, and then to N at 40 GPa. The transformation of HA to recently predicted N (N≡N-N-N=N-N-N≡N) is evident by the emergence of new peaks at 2384 cm, 1665 cm, and 1165 cm, arising from the terminal N≡N stretching, the central N=N stretching, and the N-N stretching, respectively.

Crystal structures and dynamical properties of dense CO2.

Structural polymorphism in dense carbon dioxide (CO) has attracted significant attention in high-pressure physics and chemistry for the past two decades. Here, we have performed high-pressure experiments and first-principles theoretical calculations to investigate the stability, structure, and dynamical properties of dense CO We found evidence that CO-V with the 4-coordinated extended structure can be quenched to ambient pressure below 200 K-the melting temperature of CO-I. CO-V is a fully coordinated structure formed from a molecular solid at high pressure and recovered at ambient pressure.

Pressure-induced phase and chemical transformations of lithium peroxide (Li2O2).

We present the pressure-induced phase/chemical changes of lithium peroxide (Li2O2) to 63 GPa using diamond anvil cells, confocal micro-Raman spectroscopy, and synchrotron x-ray diffraction. The Raman data show the emergence of the major vibrational peaks associated with O2 above 30 GPa, indicating the subsequent pressure-induced reversible chemical decomposition (disassociation) in dense Li2O2. The x-ray diffraction data of Li2O2, on the other hand, show no dramatic structural change but remain well within a P63/mmc structure to 63 GPa.

Pressure-induced Transformations of Dense Carbonyl Sulfide to Singly Bonded Amorphous Metallic Solid.

The application of pressure, internal or external, transforms molecular solids into non-molecular extended network solids with diverse crystal structures and electronic properties. These transformations can be understood in terms of pressure-induced electron delocalization; however, the governing mechanisms are complex because of strong lattice strains, phase metastability and path dependent phase behaviors. Here, we present the pressure-induced transformations of linear OCS (R3m, Phase I) to bent OCS (Cm, Phase II) at 9 GPa; an amorphous, one-dimensional (1D) polymer at 20 GPa (Phase III); and an extended 3D network above ~35 GPa (Phase IV) that metallizes at ~105 GPa.

Phase diagram of ammonium perchlorate: Raman spectroscopic constrains at high pressures and temperatures.

We present the pressure-temperature (PT) induced physical and chemical transformations in ammonium perchlorates (APs) up to 50 GPa and 450 °C, using diamond anvil cells and confocal micro-Raman spectroscopy, which provide new constraints for the phase diagram of AP. The results show spectral evidences for three new polymorphs (III, IV, and VI) of AP, in addition to two previously known phases (I and II), at various PT conditions with varying degrees of hydrogen bonding and lack of strong spectral evidence for previously known high-temperature cubic phase (phase V). Upon further heating, AP chemically decomposes to N2, N2O, and H2O.

Phase Diagram and Transformations of Iron Pentacarbonyl to nm Layered Hematite and Carbon-Oxygen Polymer under Pressure.

We present the phase diagram of Fe(CO)5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO)5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K.

Hydrogen bonding induced proton exchange reactions in dense D2-NH3 and D2-CH4 mixtures.

We have investigated high-pressure behaviors of simple binary mixtures of NH3 and D2 to 50 GPa and CH4 and D2 to 30 GPa using confocal micro-Raman spectroscopy. The spectral data indicate strong proton exchange reactions occur in dense D2-NH3 mixture, producing different isotopes of ammonia such as NH3, NH2D, NHD2, and ND3. In contrast, the proton exchange process in dense D2-CH4 mixture is highly limited, and no vibration feature is apparent for deuterated methane.

Phase diagram of ammonium nitrate.

Ammonium Nitrate (AN) is a fertilizer, yet becomes an explosive upon a small addition of chemical impurities. The origin of enhanced chemical sensitivity in impure AN (or AN mixtures) is not well understood, posing significant safety issues in using AN even today. To remedy the situation, we have carried out an extensive study to investigate the phase stability of AN and its mixtures with hexane (ANFO-AN mixed with fuel oil) and Aluminum (Ammonal) at high pressures and temperatures, using diamond anvil cells (DAC) and micro-Raman spectroscopy.

Superconductivity in highly disordered dense carbon disulfide.

High pressure plays an increasingly important role in both understanding superconductivity and the development of new superconducting materials. New superconductors were found in metallic and metal oxide systems at high pressure. However, because of the filled close-shell configuration, the superconductivity in molecular systems has been limited to charge-transferred salts and metal-doped carbon species with relatively low superconducting transition temperatures.

Physical and chemical transformations of highly compressed carbon dioxide at bond energies.

Carbon dioxide exhibits a richness of high-pressure polymorphs with a great diversity in intermolecular interaction, chemical bonding, and crystal structures. It ranges from typical molecular solids to fully extended covalent solids with crystal structures similar to those of SiO2. These extended solids of carbon dioxide are fundamentally new materials exhibiting interesting optical nonlinearity, low compressibility and high energy density.

Pressure-induced phase transition and polymerization of tetracyanoethylene (TCNE).

We have studied the pressure-induced physical and chemical transformations of tetracyanoethylene (TCNE or C6N4) in diamond anvil cells using micro-Raman spectroscopy, laser-heating, emission spectroscopy, and synchrotron x-ray diffraction. The results indicate that TCNE in a quasi-hydrostatic condition undergoes a shear-induced phase transition at 10 GPa and then a chemical change to two-dimensional (2D) C=N polymers above 14 GPa. These phase and chemical transformations depend strongly on the state of stress in the sample and occur sluggishly in non-hydrostatic conditions over a large pressure range between 7 and 14 GPa.

Formation and phase transitions of methane hydrates under dynamic loadings: compression rate dependent kinetics.

We describe high-pressure kinetic studies of the formation and phase transitions of methane hydrates (MH) under dynamic loading conditions, using a dynamic-diamond anvil cell (d-DAC) coupled with time-resolved confocal micro-Raman spectroscopy and high-speed microphotography. The time-resolved spectra and dynamic pressure responses exhibit profound compression-rate dependences associated with both the formation and the solid-solid phase transitions of MH-I to II and MH-II to III. Under dynamic loading conditions, MH forms only from super-compressed water and liquid methane in a narrow pressure range between 0.

Time- and angle-resolved x-ray diffraction to probe structural and chemical evolution during Al-Ni intermetallic reactions.

We present novel time- and angle-resolved x-ray diffraction (TARXD) capable of probing structural and chemical evolutions during rapidly propagating exothermic intermetallic reactions between Ni-Al multilayers. The system utilizes monochromatic synchrotron x-rays and a two-dimensional (2D) pixel array x-ray detector in combination of a fast-rotating diffraction beam chopper, providing a time (in azimuth) and angle (in distance) resolved x-ray diffraction image continuously recorded at a time resolution of ~30 μs over a time period of 3 ms. Multiple frames of the TARXD images can also be obtained with time resolutions between 30 and 300 μs over three to several hundreds of milliseconds.

H2O and D2 mixtures under pressure: spectroscopy and proton exchange kinetics.

We have investigated the pressure-induced spectral changes and the proton exchange reactions of D(2)-H(2)O mixtures to 64 GPa using micro-Raman spectroscopy. The results show the profound difference in the rotational and vibrational Raman spectra of hydrogen isotopes from those of the pure samples, showing the vibrational modes at higher frequencies and continuing to increase with pressure without apparent turnover. This indicates the repulsive nature of D(2)-H(2)O interaction without hydrogen bonds between the two and, thus, interstitial fillings of D(2) molecules into the bcc-like ice lattice.

"Stubborn" triaminotrinitrobenzene: unusually high chemical stability of a molecular solid to 150 GPa.

We report an unexpectedly high chemical stability of molecular solid 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) under static high pressures. In contrast to the high-pressure behavior of the majority of molecular solids, TATB remains both chemically stable and an insulator to 150 GPa--well above the predicted metallization pressure of 120 GPa. Single crystal studies have shown that TATB exhibits pressure-induced Raman changes associated with two subtle structural phase transitions at 28 and 56 GPa.