We present a systematic and comparative study of the pressure-induced solidification of 11 frequently used pressure transmitting fluids using the ruby fluorescence technique in a diamond anvil cell. These fluids are 1 : 1 and 5 : 1 iso-n pentane, 4 : 1 deuterated methanol–ethanol, 16 : 3 : 1 deuterated methanol–ethanol-water, 1 : 1 FC84-FC87 Fluorinert, Daphne 7474, silicone oil, as well as nitrogen, neon, argon and helium. The data provide practical guidelines for the use of these fluids in high pressure experiments up to 50 GPa.
A pressure transmitting medium named Daphne 7474, which solidifies at P(s)=3.7 GPa at room temperature, is presented. The value of P(s) increases almost linearly with temperature up to 6.7 GPa at 100 degrees C. The high pressure realized by a medium at the liquid state allows a higher limit of pressurization, which assures an ideal hydrostatic pressure. We show a volume change against pressure, pressure reduction from room to liquid helium temperature in a clamped piston cylinder cell, pressure distribution and its standard deviation in a diamond anvil cell, and infrared properties, which might be useful for experimental applications.
Under ambient condition PdSe2 has the PdS2-type structure. The crystal structure of PdSe2 under pressure (up to 30 GPa) was investigated at room temperature by X-ray diffraction in an energy-dispersive configuration using a diamond anvil cell with a mixture of water/ethanol/methanol as a pressure transmitting medium. A reversible structural transition from the PdS2-type to the pyrite-type structure occurs around 10 GPa, and the applied pressure reduces the spacing between adjacent 2/proportional to [PdSe2] layers of the PdS2-type structure to form the three-dimensional lattice of the pyrite-type structure. First principles and extended Hückel electronic band structure calculations were carried out to confirm the observed pressure-induced structural changes. We also examined why the isoelectronic analogues NiSe2 and PtSe2 adopt structures different from the PdS2-type structure on the basis of qualitative electronic structure considerations.
The photomagnetic properties of CoFe Prussian blue analogues arise from a photoinduced Co III (LS)-Fe II (LS) f Co II (HS)-Fe III (LS) [LS ) low spin, HS ) high spin] electron transfer accompanied by a spin state change of the cobalt and a significant expansion of the cobalt coordination sphere. The local bond-lengthening around the cobalt induces long-range structural changes that we studied by X-ray powder diffraction using synchrotron radiation. Beyond the structural characterization of an excited metastable state, the study shows how a photoinduced molecular bond-lengthening is made possible in a face-centered cubic Prussian blue analogue by the presence of [Fe(CN) 6 ] vacancies: in their vicinity, the lengthening of the cobalt to ligands bonds is easier. The excitation process starts at the cobalt neighbors of the vacancies through a continuous or secondorder transformation (in a single phase), which triggers a cooperative propagation through a first-order discontinuous transition (between two phases).
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