RESUMO
In this work, the dependence of the morphology and stability of the extended solid of carbon monoxide (CO) is correlated to the rate of transformation from the molecular CO to extended solid of CO using optical imaging, photoluminescence, Raman spectroscopy, and X-ray diffraction. The analyses show the rate and pressure of the transformation to be strongly controlled by catalytic effects, both chemical and optical. In a larger volume per reaction area, the transformation was found to require either a longer time at an elevated pressure or a higher pressure compared to a sample synthesized in a smaller volume per reaction area, leading to the conclusion that the transformation rate is slower for a sample in a larger volume per reaction area. A faster rate of transformation was also noted when the reaction area of a CO sample was catalyzed with H2SO4. Through variation of the volume per reaction area, pressure or the addition of catalysts, it was possible to control the rate of the phase transition and therefore the morphology. In general, the extended solid of CO synthesized with a faster rate showed a more ordered structure and increased metastability relative to the material formed with a slower compression rate.
RESUMO
The high-pressure behavior of 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (LLM-172) has been studied to 36 GPa by Raman spectroscopy and 50 GPa by X-ray diffraction. The Raman spectra and calculated unit-cell volumes at select pressures show reasonable qualitative agreement with first-principles density functional theory calculations. Raman peaks exhibit a gradual broadening and loss of intensity upon compression to near 20 GPa. Above 20 GPa, most Raman features disappear with the exception of modes associated with the skeletal ring modes. These modes were found to persist (although with low intensity) to 36 GPa. Because these modes exhibit very low compressibility over the pressure range studied, it is speculated that the ring structure is very stable. The X-ray diffraction suggests that while the crystal maintains an orthorhombic structure to near 40 GPa, it gradually undergoes a decomposition/amorphization beginning near 10 GPa. Analysis of the Raman results suggests that decomposition proceeds through isomerization, which leads to the formation of a C-O-N-O group rather than ring cleavage.
RESUMO
Biuret (C2H5N3O2) has been studied to 30 GPa by Raman spectroscopy and 50 GPa by X-ray diffraction. Raman peaks exhibit shoulders and splitting that suggests that the molecules undergo reorientation in response to compression. These are observed in three pressure ranges: the first from 3-5 GPa, the second from 8-12 GPa, and finally from 16-20 GPa. The particular modes in the sample that are observed to change in the Raman are strongly linked to the molecular vibrations involving the N-H and the CâO bond, which are most strongly coupled to the hydrogen-bonded lattice structure. The X-ray diffraction suggests that the crystal maintains a monoclinic structure to the highest pressures studied. Although there was a considerable degree of hysteresis observed in some X-ray runs, all the changes observed under pressure are reversible.
RESUMO
Cyanoacetohydrazide (CAH, C3H5N3O) has been studied under pressure using diamond anvil cell techniques. CAH was characterized using Raman spectroscopy to 30 GPa and synchrotron X-ray diffraction to 45 GPa. The Raman spectra of CAH show reasonable qualitative agreement with first-principle calculations. The X-ray data reveal that CAH maintains its monoclinic structure to approximately 22 GPa with a density change of 12% over this range. Near 22 GPa, the Raman modes and most of the X-ray diffraction peaks disappear. These pressure-induced changes are irreversible upon the release of pressure, and the transformed sample can be recovered to ambient pressure. The recovered sample is photosensitive and shows reaction even at low laser powers of 10 mW at 532 nm. The paper concludes with observations of the roles of hydrogen bonding, molecular configurations, and the behavior of the cyano group in the pressure-induced changes in CAH.
