The behavior of a number of commonly used pressure media, including nitrogen, argon, 2‐propanol, a 4:1 methanol–ethanol mixture, glycerol and various grades of silicone oil, has been examined by measuring the X‐ray diffraction maxima from quartz single crystals loaded in a diamond‐anvil cell with each of these pressure media in turn. In all cases, the onset of non‐hydrostatic stresses within the medium is detectable as the broadening of the rocking curves of X‐ray diffraction peaks from the single crystals. The onset of broadening of the rocking curves of quartz is detected at ∼9.8 GPa in a 4:1 mixture of methanol and ethanol and at ∼4.2 GPa in 2‐propanol, essentially at the same pressures as the previously reported hydrostatic limits determined by other techniques. Gigahertz ultrasonic interferometry was also used to detect the onset of the glass transition in 4:1 methanol–ethanol and 16:3:1 methanol–ethanol–water, which were observed to support shear waves above ∼9.2 and ∼10.5 GPa, respectively, at 0.8–1.2 GHz. By contrast, peak broadening is first detected at ∼3 GPa in nitrogen, ∼1.9 GPa in argon, ∼1.4 GPa in glycerol and ∼0.9 GPa in various grades of silicone oil. These pressures, which are significantly lower than hydrostatic limits quoted in the literature, should be considered as the practical maximum limits to the hydrostatic behavior of these pressure media at room temperature.
Pressure-induced transformations between gauche-, gauche+ and transoid conformations have been evidenced by X-ray single-crystal diffraction for 1,1,2-trichloroethane, and the energies of intermolecular interactions, conformational conversion, and the latent heat have been determined.
Directional Cl···Cl type I and II interactions govern the low-density aggregation of 1,1,2,2-tetrachloroethane molecules in synclinal conformation in the crystalline state at low temperature, whereas the dense molecular packing in high-pressure is achieved for the antiperiplanar conformers and electrostatically less favored Cl···Cl contacts. The mechanism of transformation between loose and dense associations involves the collapse of Cl···Cl contacts and conformational conversion.
We study experimentally and theoretically discrete solitons in crystalline structures consisting of several tens of laser-cooled ions confined in a radio frequency trap. Resonantly exciting localized, spectrally gapped vibrational modes of the soliton, a nonlinear mechanism leads to a nonequilibrium steady state of the continuously cooled crystal. We find that the propagation and the escape of the soliton out of its quasi-one-dimensional channel can be described as a thermal activation mechanism. We control the effective temperature of the soliton's collective coordinate by the amplitude of the external excitation. Furthermore, the global trapping potential permits controlling the soliton dynamics and realizing directed transport depending on its topological charge.
Isochoric and isobaric freezing of 1,1-dichloroethane, CH3CHCl2, mp=176.19 K, yielded the orthorhombic structure, space group Pnma, with the fully ordered molecules, in the staggered conformation, located on mirror planes. The CH3CHCl2 ambient-pressure (0.1 MPa) structures were determined at 160 and 100 K, whereas the 295 K high-pressure structures were determined at 0.59 and 1.51 GPa. At 0.1 MPa, all intermolecular distances are considerably longer than the sums of the van der Waals radii, and only a pressure of about 1.5 GPa squeezed the Cl...Cl and Cl...H contacts to distances commensurate with these sums. The exceptionally large difference between the melting points of isomeric 1,1- and 1,2-dichloroethane can be rationalized in terms of their molecular-packing efficiency. It has been shown that the location of atoms in molecules affects their intermolecular interactions, and hence their van der Waals radii are the function of molecular structures.
Low-density liquids and solids, with all intermolecular contacts longer than the sum of van der Waals radii, are formed by all ethanes chlorinated at one locant: CH 2 ClCH 3 , CHCl 2 CH 3 and CCl 3 CH 3 . The concepts of molecular symmetry described by Carnelley and that of point groups have been compared. Carnelley's rule, when applied to liquid and solid chloroethanes clearly reveals the density dependence on the presence of intermolecular Cl … Cl and H … Cl short contacts, or their absence due to steric hindrances of overcrowded substituents. At 2.62 GPa, CH 2 ClCH 3 freezes directly into phase II, with molecules arranged into layers with short Cl … Cl, H … Cl and H … H contacts. Only for CH 2 ClCH 3 , both the low-density phase at low temperature and closely-packed phase above 2.62 GPa have been observed.
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