Daniel Sneed

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.

Inner-shell Chemistry under High Pressure

Chemistry at ambient conditions has implicit boundaries rooted in the atomic shell structure: the inner-shell electrons and the unoccupied outer-shell orbitals do not contribute as the major component to chemical reactions and in chemical bonds. These general rules govern our understanding of chemical structures and reactions. We review the recent progresses in high-pressure chemistry demonstrating that the above rules can be violated under extreme conditions. Using a first principles computation method and crystal structure search algorithm, we demonstrate that stable compounds involving inner shell electrons such as CsF3, CsF5, HgF3, and HgF4 can form under high external pressure and may present exotic properties. We also discuss experimental studies that have sought to confirm these predictions. Employing our recently developed hard X-ray photochemistry methods in a diamond anvil cell, we show promising early results toward realizing inner shell chemistry experimentally.

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.

Studies in useful hard x-ray photochemistry: decomposition of potassium halates

We performed a systematic study of radiation-induced decomposition rates of KClO3, KClO4, KBrO3 and KIO3 in glass capillaries using the monochromatic x-ray. We also performed a complementary white beam x-ray study to verify the presence of molecular oxygen released from the acatalytic, isothermal chemical reactions initiated by hard x-rays using a diamond anvil cell to seal the samples. The aim of these studies entailed better-understanding the effect of oxygen-oxygen distance and oxygen multiplicity in determining the x-ray induced decomposition rate of potassium halates to aid useful hard x-ray induced chemistry. The observed decomposition rate appears to strongly and inversely correlate with O-O distance which suggests that ionization events of oxygen atoms from the halate groups occur nearly simultaneously and irreversible chemical reaction of two ionized oxygen radicals occurs with a higher probability when they are closer to one another.

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.

A Novel Method for Generating Molecular Mixtures at Extreme Conditions: The Case of Fluorine and Oxygen

We have successfully created a segregated mixture of molecular fluorine and oxygen at high pressure in a diamond anvil cell (DAC) via useful hard x-ray photochemistry. A keyhole-like sample chamber was created in a stainless steel gasket to hold two segregated powders of potassium tetrafluoroborate (KBF4) and potassium perchlorate (KClO4) respectively in each hole at a pressure of ∼3.0 GPa. Both holes were individually irradiated with synchrotron hard x-rays to release molecular fluorine and molecular oxygen, respectively. Upon irradiation of the hole containing KBF4 molecular fluorine appeared (as evidenced via Raman spectroscopy) near the region of irradiation. The second hole containing KClO4 was then irradiated and reddish-orange O2 was observed to form. Oxygen was observed to diffuse throughout both holes. There is some evidence that oxygen difluoride (OF2) was formed in the hole originally containing the KBF4.

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.

A novel synthesis of polymeric CO via useful hard x-ray photochemistry

Abstract We report on the synchrotron hard X-ray-induced decomposition of strontium oxalate (SrC2O4) pressurized to 7 GPa inside a diamond anvil cell (DAC). After some 4 h of irradiation in a white X-ray synchrotron beam, a dark reddish/brown region formed in the area of irradiation which was surrounded by a yellowish brown remainder in the rest of the sample. Upon depressurization of the sample to ambient conditions, the reacted/decomposed sample was recoverable as a dark brown/red and yellow waxy solid. Synchrotron infrared spectroscopy confirmed the strong presence of CO2 even under ambient conditions with the sample exposed to air and other strongly absorbing regions, suggesting that the sample may likely be polymerized CO (in part) with dispersed CO2 and SrO trapped within the polymer. These results will have significant implications in the ability to readily produce and trap CO2 in situ via irradiation of a simple powder for useful hard X-ray photochemistry and in the ability to easily manufacture polymeric CO (via loading of powders in a DAC or high volume press) without the need for the dangerous and complex loading of toxic CO. A novel means of X-ray-induced polymerization under extreme conditions has also been demonstrated.

High-Pressure Equation of State of Cesium Fluoride to 120 GPa

We have performed a high pressure synchrotron x-ray diffraction study of the ionic salt, cesium fluoride (CsF), up to 120 GPa. We observed the B1 → B2 phase transition near 5 GPa as previously reported. Beyond this pressure, no phase transitions were determined to have occurred up to the highest pressure studied. Unit cell data were calculated from the known B2 (CsCl) structure for all of the pressures studied above 5 GPa, and an equation of state (EOS) was fit to the data using a 3rd order Birch-Murnaghan equation in this phase. Density Functional Theory (DFT) was also employed to compute an EOS for comparison purposes. Our experimental results agreed very well with both sets of the predicted EOS.

Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure

This paper discusses our attempt to synthesize higher oxidation forms of cesium fluoride by pressurizing cesium fluoride in a fluorine-rich environment created via the x-ray decomposition of potassium tetrafluoroborate. This was done in order to confirm recent theoretical predictions of higher oxidation forms of CsFn. We discuss the development of a technique to produce molecular fluorine in situ via useful hard x-ray photochemistry, and the attempt to utilize this technique to form higher oxidation states of cesium fluoride. In order to verify the formation of the novel stoichiometric species of CsFn. X-ray Absorption Near Edge Spectroscopy (XANES) centered on the cesium K-edge was performed to probe the oxidation state of cesium as well as the local molecular coordination around Cs.