Static compression of tetramethylammonium borohydride.

Raman spectroscopy and synchrotron X-ray diffraction are used to examine the high-pressure behavior of tetramethylammonium borohydride (TMAB) to 40 GPa at room temperature. The measurements reveal weak pressure-induced structural transitions around 5 and 20 GPa. Rietveld analysis and Le Bail fits of the powder diffraction data based on known structures of tetramethylammonium salts indicate that the transitions are mediated by orientational ordering of the BH(4)(-) tetrahedra followed by tilting of the (CH(3))(4)N(+) groups. X-ray diffraction patterns obtained during pressure release suggest reversibility with a degree of hysteresis. Changes in the Raman spectrum confirm that these transitions are not accompanied by bonding changes between the two ionic species. At ambient conditions, TMAB does not possess dihydrogen bonding, and Raman data confirms that this feature is not activated upon compression. The pressure-volume equation of state obtained from the diffraction data gives a bulk modulus [K(0) = 5.9(6) GPa, K(0)' = 9.6(4)] slightly lower than that observed for ammonia borane. Raman spectra obtained over the entire pressure range (spanning over 40% densification) indicate that the intramolecular vibrational modes are largely coupled.

Anomalous compression behavior in lanthanum/cerium-based metallic glass under high pressure.

In situ high-pressure x-ray diffraction, low-temperature resistivity, and magnetization experiments were performed on a La(32)Ce(32)Al(16)Ni(5)Cu(15) bulk metallic glass (BMG). A sudden change in compressibility at approximately 14 GPa and a rapid increase of resistivity at approximately 12 K were detected, whereas magnetic phase transformation and magnetic field dependence of the low-temperature resistivity do not occur at temperatures down to 4.2 K. An interaction between conduction electrons and the two-level systems is suggested to explain the temperature and field dependences of resistivity of the BMG alloy. Although the cause of the unusual change in compressibility at approximately 14 GPa is not clear, we believe that it could be linked with the unique electron structure of cerium in the amorphous matrix. An electronic phase transition in BMG alloys, most likely a second-order amorphous-to-amorphous phase transition, is suggested.

Pressure-tuned spin and charge ordering in an itinerant antiferromagnet.

Elemental chromium orders antiferromagnetically near room temperature, but the ordering temperature can be driven to zero by applying large pressures. We combine diamond anvil cell and synchrotron x-ray diffraction techniques to measure directly the spin and charge order in the pure metal at the approach to its quantum critical point. Both spin and charge order are suppressed exponentially with pressure, well beyond the region where disorder cuts off such a simple evolution, and they maintain a harmonic scaling relationship over decades in scattering intensity. By comparing the development of the order parameter with that of the magnetic wave vector, it is possible to ascribe the destruction of antiferromagnetism to the growth in electron kinetic energy relative to the underlying magnetic exchange interaction.

Absence of magnetism in hcp iron-nickel at 11 K.

Synchrotron Mössbauer spectroscopy (SMS) was performed on an hcp-phase alloy of composition Fe92Ni8 at a pressure of 21 GPa and a temperature of 11 K. Density functional theoretical calculations predict antiferromagnetism in both hcp Fe and hcp Fe-Ni. For hcp Fe, these calculations predict no hyperfine magnetic field, consistent with previous experiments. For hcp Fe-Ni, however, substantial hyperfine magnetic fields are predicted, but these were not observed in the SMS spectra. Two possible explanations are suggested. First, small but significant errors in the generalized gradient approximation density functional may lead to an erroneous prediction of magnetic order or of erroneous hyperfine magnetic fields in antiferromagnetic hcp Fe-Ni. Alternately, quantum fluctuations with periods much shorter than the lifetime of the nuclear excited state would prohibit the detection of moments by SMS.

First-order isostructural Mott transition in highly compressed MnO.

We present evidence for an isostructural, first-order Mott transition in MnO at 105+/-5 GPa, based on high-resolution x-ray emission spectroscopy and angle-resolved x-ray diffraction data. The pressure-induced structural and spectral changes provide a coherent picture of MnO phase transitions from paramagnetic B1 to antiferromagnetic distorted B1 at 30 GPa, to paramagnetic B8 at 90 GPa, and to diamagnetic B8 at 105+/-5 GPa. The last is the Mott transition, accompanied by a significant loss of magnetic moment, an approximately 6.6% volume collapse and the insulator-metal transition as demonstrated by recent resistance measurements.

Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon.

Crystalline and amorphous forms of silicon are the principal materials used for solid-state electronics and photovoltaics technologies. Silicon is therefore a well-studied material, although new structures and properties are still being discovered. Compression of bulk silicon, which is tetrahedrally coordinated at atmospheric pressure, results in a transition to octahedrally coordinated metallic phases. In compressed nanocrystalline Si particles, the initial diamond structure persists to higher pressure than for bulk material, before transforming to high-density crystals. Here we report compression experiments on films of porous Si, which contains nanometre-sized domains of diamond-structured material. At pressures larger than 10 GPa we observed pressure-induced amorphization. Furthermore, we find from Raman spectroscopy measurements that the high-density amorphous form obtained by this process transforms to low-density amorphous silicon upon decompression. This amorphous-amorphous transition is remarkably similar to that reported previously for water, which suggests an underlying transition between a high-density and a low-density liquid phase in supercooled Si (refs 10, 14, 15). The Si melting temperature decreases with increasing pressure, and the crystalline semiconductor melts to a metallic liquid with average coordination approximately 5 (ref. 16).

Synthesis and characterization of a binary noble metal nitride.

There has been considerable interest in the synthesis of new nitrides because of their technological and fundamental importance. Although numerous metals react with nitrogen there are no known binary nitrides of the noble metals. We report the discovery and characterization of platinum nitride (PtN), the first binary nitride of the noble metals group. This compound can be formed above 45-50 GPa and temperatures exceeding 2,000 K, and is stable after quenching to room pressure and temperature. It is characterized by a very high Raman-scattering cross-section with easily observed second- and third-order Raman bands. Synchrotron X-ray diffraction shows that the new phase is cubic with a remarkably high bulk modulus of 372(+/-5) GPa.

Novel broken symmetry phase from N(2)O at high pressures and high temperatures.

Simple molecular solids become unstable at high pressures, typically transforming to dense framework and/or metallic structures. We report formation of an unusual ionic solid NO(+)NO(3)(-) (nitrosonium nitrate) from N(2)O at pressures above 20 GPa and temperatures above 1000 K. Synchrotron x-ray diffraction indicates that the compound crystallizes with a structure related to the aragonite form of CaCO(3) and NaNO(3). Raman and infrared spectroscopic data indicate that the structure is noncentrosymmetric and exhibits a strong pressure dependent charge transfer and orientational order.