A novel means to generate high pressure.

Diamond anvil cells are the most popular means of generating pressures above 2 GPa. However, in many experiments, such as nuclear magnetic resonance and x-ray absorption, the metallic pressurizing gasket (which confines much of the sample) represents an occluding barrier that requires a low Z gasket material (e.g., Be), a split gasket, or other means to enable better coupling of the sample to electromagnetic radiation. In this paper, we demonstrate a novel method for generating high pressures that confines the sample just above the plane of the gasket by using a diamond with a laser hole drilled into the center of the tip. The sample is then confined by the hole, which is sealed by a flat gasket that fits over the hole. When load is applied to the diamonds, metal flows from the deformed gasket into the hole thereby pressurizing the sample similarly to how a piston pressurizes gas inside a cylinder. The pressurized sample is above the metallic gasket plane just inside the tip of the diamond, and thus easily accessible via x rays or visible light that skims just above the plane of the gasket providing an enhanced aperture of radiation collection. We have demonstrated the utility of this method by obtaining Raman spectra of SnC2O4 and x-ray diffraction spectra of seleno-DL-cystine, all at high pressures.

Experimental demonstration of necessary conditions for X-ray induced synthesis of cesium superoxide.

Absorption of sufficiently energetic X-ray photons by a molecular system results in a cascade of ultrafast electronic relaxation processes which leads to a distortion and dissociation of its molecular structure. Here, we demonstrate that only decomposition of powdered cesium oxalate monohydrate induced by monochromatic X-ray irradiation under high pressure leads to the formation of cesium superoxide. Whereas, for an unhydrated form of cesium oxalate subjected to the same extreme conditions, only degradation of the electron density distribution is observed. Moreover, the corresponding model of X-ray induced electronic relaxation cascades with an emphasis on water molecules' critical role is proposed. Our experimental results suggest that the presence of water molecules in initially solid-state systems (i.e. additional electronic relaxation channels) together with applied high pressure (reduced interatomic/intermolecular distance) could potentially be a universal criteria for chemical and structural synthesis of novel compounds via X-ray induced photochemistry.

Observation of pressure-induced electron transfer in SnC2O4.

We examined the high pressure behavior of stannous oxalate via Raman and X-ray absorption spectroscopy (XAS) inside a diamond anvil cell. Phase transitions were observed to occur near 2.6 and 15 GPa which were reversible upon decompression to ambient conditions. When further pressurized above 15 GPa, the colorless material sustains irreversible chemical alterations and becomes bright red colored - darkening at higher pressures. Another irreversible phase transition occurred above 20 GPa. Concomitant with color change of the sample, we observed a softening of the ν(C-C) modes of the C2O42- anion via Raman spectroscopy. We performed a separate XAS experiment which indicates that the Sn2+ cation undergoes a partial reduction of the 2+ oxidation state with pressure which persists when the sample was depressurized to ambient conditions. Thus, electron density within the C-C bond in the oxalate anion appears to migrate toward the tin cation with pressure. This observation suggests that pressure can offer a very controllable means to vary cation-anion and unit cell dimensions (and thus the electric interactions causing electron movement) and thus the pressure-induced synthesis of novel materials.

Cationic Dependence of X-ray Induced Damage in Strontium and Barium Nitrate.

The response of solids to X-ray irradiation is not well understood in part because the interactions between X-rays and molecules in solids depend on the intra- and/or intermolecular electronic properties of the material. Our previous work demonstrated that X-ray induced damage of certain ionic salts depends on the irradiating photon energy, especially when irradiated with photons of energy near the cation's K-edge. To advance understanding of the cationic dependence of X-ray photochemistry, we present studies of X-ray induced damage of barium nitrate and strontium nitrate. Polycrystalline samples of barium and strontium nitrate were irradiated with high flux monochromatic synchrotron X-rays at selected energies near the K-edge of the respective cations. The damage processes were studied with powder X-ray diffraction, and irradiation products, NO2 and O2, were characterized via Raman spectroscopy. Our results demonstrate that irradiating barium and strontium nitrate with photons of energy greater than the K-edge of the cation promotes a higher rate of decomposition compared to that observed when irradiating with photons of energy below the K-edge. Additionally, differences in X-ray induced damage between the two compounds are examined and discussed, and evidence of the diffusion of irradiation products is presented.

High-pressure-assisted X-ray-induced damage as a new route for chemical and structural synthesis.

X-ray induced damage has been known for decades and has largely been viewed as a tremendous nuisance. We, on the other hand, harness the highly ionizing and penetrating properties of hard X-rays to initiate novel decomposition and synthetic chemistry. Here, we show that powdered cesium oxalate monohydrate pressurized to ≤0.5 GPa and irradiated with X-rays of energies near the cesium K-edge undergoes molecular and structural transformations with one of the final products exhibiting a new type of bcc crystal structure that has previously not been observed. Additionally, based on cascades of ultrafast electronic relaxation steps triggered by the absorption of one X-ray photon, we propose a model explaining the X-ray induced damage of multitype bounded matter. As X-rays are ubiquitous, these results show promise in the preparation of novel compounds and novel structures that are inaccessible via conventional methods. They may offer insight into the formation of complex organic compounds in outer space.

Measurement of the Energy and High-Pressure Dependence of X-ray-Induced Decomposition of Crystalline Strontium Oxalate.

We report measurements of the X-ray-induced decomposition of crystalline strontium oxalate (SrC2O4) as a function of energy and high pressure in two separate experiments. SrC2O4 at ambient conditions was irradiated with monochromatic synchrotron X-rays ranging in energy from 15 to 28 keV. A broad resonance of the decomposition yield was observed with a clear maximum when irradiating with ∼20 keV X-rays and ambient pressure. Little or no decomposition was observed at 15 keV, which is below the Sr K-shell energy of 16.12 keV, suggesting that excitation of core electrons may play an important role in the destabilization of the C2O42- anion. A second experiment was performed to investigate the high-pressure dependence of the X-ray-induced decomposition of strontium oxalate at fixed energy. SrC2O4 was compressed in a diamond anvil cell (DAC) in the pressure range from 0 to 7.6 GPa with 1 GPa increments and irradiated in situ with 20 keV X-rays. A marked pressure dependence of the decomposition yield of SrC2O4 was observed with a decomposition yield maximum at around 1 GPa, suggesting that different crystal structures of the material play an important role in the decomposition process. This may be due in part to a phase transition observed near this pressure.

Pressure-Driven Cooperative Spin-Crossover, Large-Volume Collapse, and Semiconductor-to-Metal Transition in Manganese(II) Honeycomb Lattices.

Spin-crossover (SCO) is generally regarded as a spectacular molecular magnetism in 3d4-3d7 metal complexes and holds great promise for various applications such as memory, displays, and sensors. In particular, SCO materials can be multifunctional when a classical light- or temperature-induced SCO occurs along with other cooperative structural and/or electrical transport alterations. However, such a cooperative SCO has rarely been observed in condensed matter under hydrostatic pressure (an alternative external stimulus to light or temperature), probably due to the lack of synergy between metal neighbors under compression. Here, we report the observation of a pressure-driven, cooperative SCO in the two-dimensional (2D) honeycomb antiferromagnets MnPS3 and MnPSe3 at room temperature. Applying pressure to this confined 2D system leads to a dramatic magnetic moment collapse of Mn2+ (d5) from S = 5/2 to S = 1/2. Significantly, a number of collective phenomena were observed along with the SCO, including a large lattice collapse (∼20% in volume), the formation of metallic bonding, and a semiconductor-to-metal transition. Experimental evidence shows that all of these events occur in the honeycomb lattice, indicating a strongly cooperative mechanism that facilitates the occurrence of the abrupt pressure-driven SCO. We believe that the observation of this cooperative pressure-driven SCO in a 2D system can provide a rare model for theoretical investigations and lead to the discovery of more pressure-responsive multifunctional materials.

Giant Pressure-Driven Lattice Collapse Coupled with Intermetallic Bonding and Spin-State Transition in Manganese Chalcogenides.

Materials with an abrupt volume collapse of more than 20 % during a pressure-induced phase transition are rarely reported. In such an intriguing phenomenon, the lattice may be coupled with dramatic changes of orbital and/or the spin-state of the transition metal. A combined in situ crystallography and electron spin-state study to probe the mechanism of the pressure-driven lattice collapse in MnS and MnSe is presented. Both materials exhibit a rocksalt-to-MnP phase transition under compression with ca. 22 % unit-cell volume changes, which was found to be coupled with the Mn(2+) (d(5) ) spin-state transition from S=5/2 to S=1/2 and the formation of Mn-Mn intermetallic bonds as supported by the metallic transport behavior of their high-pressure phases. Our results reveal the mutual relationship between pressure-driven lattice collapse and the orbital/spin-state of Mn(2+) in manganese chalcogenides and also provide deeper insights toward the exploration of new metastable phases with exceptional functionalities.

Reversible switching between pressure-induced amorphization and thermal-driven recrystallization in VO2(B) nanosheets.

Pressure-induced amorphization (PIA) and thermal-driven recrystallization have been observed in many crystalline materials. However, controllable switching between PIA and a metastable phase has not been described yet, due to the challenge to establish feasible switching methods to control the pressure and temperature precisely. Here, we demonstrate a reversible switching between PIA and thermally-driven recrystallization of VO2(B) nanosheets. Comprehensive in situ experiments are performed to establish the precise conditions of the reversible phase transformations, which are normally hindered but occur with stimuli beyond the energy barrier. Spectral evidence and theoretical calculations reveal the pressure-structure relationship and the role of flexible VOx polyhedra in the structural switching process. Anomalous resistivity evolution and the participation of spin in the reversible phase transition are observed for the first time. Our findings have significant implications for the design of phase switching devices and the exploration of hidden amorphous materials.

Hexafluorobenzene under Extreme Conditions.

We report the results from three high pressure experiments on hexafluorobenzene (C6F6). In the first experiment, Raman spectra were recorded up to 34.4 GPa. A phase transition from I → II was observed near 2 GPa. Near 8.8 GPa, a phase transition to an unreported phase (III) commenced. Above 20.6 GPa, yet another phase was observed (IV). Pressure cycling was employed to determine that, below 25.6 GPa, all pressure-induced alterations were reversible. However, at pressures above 20 GPa, dramatic spectral changes and broadening were observed at 25.6 and 34.4 GPa. The sample irreversibly changed into a soft solid with waxlike consistency when pressure was reduced to ambient and was recoverable. In the second experiment, IR spectra were collected up to 14.6 GPa. The phase transition (II → III) near 8.8 GPa was confirmed. An angular dispersive X-ray diffraction experiment was conducted to 25.6 GPa. Phase transitions above 1.4 GPa (I → II), above 5.5 GPa (II → III), above 10 GPa (III → IV), and above 15.5 GPa (IV → V) were observed. Near 25.6 GPa, long-range crystalline order was lost as the X-ray diffraction spectrum presented evidence of an amorphous solid.

Communication: A novel method for generating molecular mixtures at extreme conditions: the case of hydrogen and oxygen.

We have successfully created a segregated mixture of hydrogen and oxygen at high pressure in a diamond anvil cell using hard x-ray photochemistry. A keyhole (two holes connected by an opening) sample chamber was created in a metallic gasket to support two segregated powders of ammonia borane and potassium perchlorate, respectively, in each hole at a pressure of ~5.0 GPa. Both holes were separately irradiated with synchrotron hard x-rays to release molecular oxygen and molecular hydrogen, respectively. Upon irradiation of the first KClO4-containing hole, solid reddish-orange O2 appeared in the region of irradiation and molecular oxygen was found to diffuse throughout the entire sample region. The second ammonia borane-containing hole was then irradiated and H2 was observed to form via Raman spectroscopy. Water also was observed in the ammonia borane-containing hole and possibly (in the form of ice VII) in the second hole. This unique experiment demonstrates the ability to easily create solid mixtures of simple molecular systems via x-ray irradiation and then react them via further irradiation which will aid the study of chemistry under extreme conditions.

Note: Loading method of molecular fluorine using x-ray induced chemistry.

We have successfully loaded molecular fluorine into a diamond anvil cell at high pressure using the synchrotron x-ray induced decomposition of perfluorohexane (C6F14). "White" x-ray radiation from the Advanced Photon Source was used to initiate the chemical decomposition of C6F14, which resulted in the in situ production of F2 as verified via Raman spectroscopy. Due to the toxic nature of fluorine, this method will offer significant advantages in the ability to easily load a relatively nontoxic and inert substance into a chamber (such as a diamond anvil cell) that, when sealed with other reactants and irradiate with hard x-rays (>7 keV), releases highly reactive and toxic fluorine into the sample/reaction chamber to enable novel chemical synthesis under isolated and/or extreme conditions.

Carbon tetrachloride under extreme conditions.

We report on three experiments on carbon tetrachloride subjected to extreme conditions. In the first experiment, Raman spectra of CCl4 were acquired up to 28 GPa. Evidence was observed for at least two new phases of CCl4 above 14 GPa (phase VI) and above 22 GPa (phase VII). Decompression of the sample showed no evidence of pressure-induced decomposition. In the second experiment, a synchrotron x-ray diffraction study was performed up to 30 GPa verifying phase V and potential phases above 14 (VI) and 22 GPa (VII), respectively. In the third study, we examined irradiated CCl4 using synchrotron infrared spectroscopy to reduce fluorescent contamination. Some sort of carbon allotrope appears as a byproduct suggesting the following reaction with hard x-rays: CCl4+ hν → C + 2Cl2.

Measurement of the energy dependence of X-ray-induced decomposition of potassium chlorate.

We report the first measurements of the X-ray induced decomposition of KClO3 as a function of energy in two experiments. KClO3 was pressurized to 3.5 GPa and irradiated with monochromatic synchrotron X-rays ranging in energy from 15 to 35 keV in 5 keV increments. A systematic increase in the decomposition rate as the energy was decreased was observed, which agrees with the 1/E(3) trend for the photoelectric process, except at the lowest energy studied. A second experiment was performed to access lower energies (10 and 12 keV) using a beryllium gasket; suggesting an apparent resonance near 15 keV or 0.83 Ǻ maximizing the chemical decomposition rate. A third experiment was performed using KIO3 to ascertain the anionic dependence of the decomposition rate, which was observed to be far slower than in KClO3, suggesting that the O-O distance is the critical factor in chemical reactions. These results will be important for more efficiently initiating chemical decomposition in materials using selected X-ray wavelengths that maximize decomposition to aid useful hard X-ray-induced chemistry and contribute understanding of the mechanism of X-ray-induced decomposition of the chlorates.

1,1-Diamino-2,2-dinitroethylene under high pressure-temperature.

The structural phase stability of 1,1-diamino-2,2-dinitroethylene (FOX-7) has been studied up to 10 GPa through isothermal compression at 100 °C and 200 °C using synchrotron mid- and far-infrared spectroscopy. During isothermal compression at 100 °C changes are observed in vibrational spectra with increase in pressure that are indicative of significant distortion to monoclinic α phase or a possible structural transformation to a high pressure α(') phase at 2.2 GPa and α(") phase at 6.1 GPa. At 200 °C, for the far- and mid-IR regimes, the similar changes were observed at 2.1 (2.0) GPa and 5.3 (5.5) GPa, respectively. The observed change is nearly isobaric, consistent with previously reported high pressure and room temperature values, up to the highest temperature of 200 °C reached in our experiments. Over the total P-T range investigated, up to ∼10 GPa and 200 °C, we observed no evidence of sample decomposition. The observed changes are partially reversible with only slight evidence of the high pressure distortion remaining upon complete decompression. Additional isobaric heating at 1.07 GPa was performed in the mid-IR regime, which clearly revealed an onset of decomposition at 360 °C. Further x-ray or neutron diffraction, which are needed to fully resolve the cause of observed changes above 2 and 5 GPa, are ongoing.

Charge transfer in spinel Co3O4 at high pressures.

Charge transfer in cobalt oxide Co(3)O(4) in the spinel structure is evidenced by experimental results using x-ray diffraction (XRD), x-ray absorption near edge structure (XANES) spectroscopy, and Raman scattering at high pressures up to 42.1, 24.6 and 35.1 GPa, respectively. While the cubic structure was found to persist under pressure up to 42.1 GPa based on the XRD and Raman results, the mode Grüneisen parameter was calculated according to our Raman measurements. Our structural data refinement revealed a structural transition from the normal spinel structure at low pressures to a partially inverse spinel structure at pressures above 17.7 GPa. This transition may be caused by the interaction of charges between tetrahedral and octahedral sites via a charge transfer process. Evidence for the charge transfer process is further supported by changes of the pre-edge features in the XANES data.

Note: Experiments in hard x-ray chemistry: in situ production of molecular hydrogen and x-ray induced combustion.

We have successfully loaded H(2) into a diamond anvil cell at high pressure using the synchrotron x-ray induced decomposition of NH(3)BH(3). In a second set of studies, radiation-assisted release of O(2) from KCLO(3), H(2) release from NH(3)BH(3), and reaction of these gases in a mixture of the reactants to form liquid water using x-rays at ambient conditions was observed. Similar observations were made using a KCLO(3) and NaBH(4) mixture. Depending on reaction conditions, an explosive or far slower reaction producing water was observed.

Note: A novel method for in situ loading of gases via x-ray induced chemistry.

We have developed and demonstrated a novel method to load oxygen in a sealed diamond anvil cell via the x-ray induced decomposition of potassium chlorate. By irradiating a pressurized sample of an oxidizer (KClO(3)) with either monochromatic or white beam x-rays from the Advanced Photon Source at ambient temperature and variable pressure, we succeeded in creating a localized region of molecular oxygen surrounded by unreacted sample which was confirmed via Raman spectroscopy. We anticipate that this technique will be useful in loading even more challenging, difficult-to-load gases such as hydrogen and also to load multiple gases.

High-pressure far- and mid-infrared study of 1,3,5-triamino-2,4,6-trinitrobenzene.

Synchrotron infrared measurements of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) have been performed in the far-IR and mid-IR spectral regions up to approximately 30 and approximately 40 GPa, respectively. For the far-IR experiment, no pressurizing medium was used, whereas KBr was utilized as a pressurizing medium for the mid-IR experiment. For both experiments, pressure was cycled and IR spectra were recorded at various pressures to ascertain sample survival. In the high frequency region (approximately 3000 cm(-1)) of the mid-IR spectra, the peak frequencies of the NH2 symmetric and antisymmetric vibrational modes steadily decrease with increasing pressure, indicating strengthening of intermolecular hydrogen bonding with pressure. In both experiments, no apparent phase transition was observed to the highest pressures studied.

Raman spectroscopic study of cyclopentane at high pressure.

The behavior of cyclopentane with pressure has been investigated to 21.5 GPa using Raman spectroscopy. Various phases were observed with pressure which included liquid, two plastic, and one true crystalline phases of cyclopentane during compression and decompression sequences. Optimized molecular structure and Raman and IR vibrational spectra of the most stable puckered-ring conformation of the cyclopentane molecule were also computed using density functional theory methods. The theoretically calculated values as well as the experimentally determined pressure dependencies of spectral bands are in very good agreement with the low temperature measurements and previous mode assignments. The phase diagram of cyclopentane was analyzed with respect to pressure-induced alterations in Raman spectra across the phase boundaries. The various forms of "frozen-in" conformations in phase III are suggested to explain previous results related to existence of a "new" phase between plastic crystalline phase II and monoclinic phase III in solid cyclopentane.