Pressure-induced phase transition in the electronic structure of palladium nitride

We present a combined theoretical and experimental study of the electronic structure and equation of state (EOS) of crystalline PdN2. The compound forms above 58 GPa in the pyrite structure and is metastable down to 11 GPa. We show that the EOS cannot be accurately described within either the local density or generalized gradient approximations. The Heyd-Scuseria-Ernzerhof exchange-correlation functional (HSE06), however, provides very good agreement with experimental data. We explain the strong pressure dependence of the Raman intensities in terms of a similar dependence of the calculated band gap, which closes just below 11 GPa. At this pressure, the HSE06 functional predicts a first-order isostructural transition accompanied by a pronounced elastic instability of the longitudinal-acoustic branches that provides the mechanism for the experimentally observed decomposition. Using an extensive Wannier function analysis, we show that the structural transformation is driven by a phase transition of the electronic structure, which is manifested by a discontinuous change in the hybridization between Pd-d and N-p electrons as well as a conversion from single to triple bonded nitrogen dimers. We argue for the possible existence of a critical point for the isostructural transition, at which massive fluctuations in both the electronic as well as the structural degrees of freedom are expected.Comment: 9 pages, 12 figures. Revised version corrects minor typographical error

High-Pressure Synthesis of a Pentazolate Salt

The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5-, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms to N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. This work provides a critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species

Elastic constants of B-HMX and tantalum, equations of state of supercritical fluids and fluid mixtures and thermal transport determinations

Ultrasonic sound speed measurements via Impulsive Stimulated Light Scattering (ISLS) were made in single crystals of b-HMX and tantalum over an extended range of temperatures. Elastic constants are consequently determined for b-HMX. Sound speeds are calculated for tantalum, from known elastic constants, and compare favorably with the results presented here. ISLS time-domain fits of tantalum records allowed for thermal diffusion determinations and, correspondingly, thermal conductivity. Measurements of the speed of sound and of the thermal diffusivities of fluid oxygen up to pressures of 13 GPa and at several temperatures are presented. Between 0.1 and 13 GPa the fluid's density increases by a factor of three. Thermal diffusivities rise slowly over this range, and are substantially smaller than those previously measured for the solid b-phase. Additional sound speed measurements were made along the 250 C isotherm in a 1:1 molar ratio mixture of liquid oxygen and nitrogen. These experiments demonstrate the versatility and potential application of a new laboratory within the U. S. DOD and DOE complex.

Tetrahymena thermophila and Candida albicans Group I intron-derived ribozymes can catalyze the trans-excision-splicing reaction

Group I intron-derived ribozymes can catalyze a variety of non-native reactions. For the trans-excision-splicing (TES) reaction, an intron-derived ribozyme from the opportunistic pathogen Pneumocystis carinii catalyzes the excision of a predefined region from within an RNA substrate with subsequent ligation of the flanking regions. To establish TES as a general ribozyme-mediated reaction, intron-derived ribozymes from Tetrahymena thermophila and Candida albicans, which are similar to but not the same as that from Pneumocystis, were investigated for their propensity to catalyze the TES reaction. We now report that the Tetrahymena and Candida ribozymes can catalyze the excision of a single nucleotide from within their ribozyme-specific substrates. Under the conditions studied, the Tetrahymena and Candida ribozymes, however, catalyze the TES reaction with lower yields and rates [Tetrahymena (kobs) = 0.14/min and Candida (kobs) = 0.34/min] than the Pneumocystis ribozyme (kobs = 3.2/min). The lower yields are likely partially due to the fact that the Tetrahymena and Candida catalyze additional reactions, separate from TES. The differences in rates are likely partially due to the individual ribozymes ability to effectively bind their 3′ terminal guanosines as intramolecular nucleophiles. Nevertheless, our results demonstrate that group I intron-derived ribozymes are inherently able to catalyze the TES reaction

Many Disease-Associated Variants of hTERT Retain High Telomerase Enzymatic Activity

Mutations in the gene for telomerase reverse transcriptase (hTERT) are associated with diseases including dyskeratosis congenita, aplastic anemia, pulmonary fibrosis and cancer. Understanding the molecular basis of these telomerase-associated diseases requires dependable quantitative measurements of telomerase enzyme activity. Furthermore, recent findings that the human POT1-TPP1 chromosome end-binding protein complex stimulates telomerase activity and processivity provide incentive for testing variant telomerases in the presence of these factors. In the present work, we compare multiple disease-associated hTERT variants reconstituted with the RNA subunit hTR in two systems (rabbit reticulocyte lysates and human cell lines) with respect to telomerase enzymatic activity, processivity and activation by telomere proteins. Surprisingly, many of the previously reported disease-associated hTERTalleles give near-normal telomerase enzyme activity. It is possible that a small deficit in telomerase activity is sufficient to cause telomere shortening over many years. Alternatively, mutations may perturb functions such as the recruitment of telomerase to telomeres, which are essential in vivo but not revealed by simple enzyme assays

Deflagration Rates and Molecular Bonding Trends of Statically Compressed Secondary Explosives

We discuss our measurements of the chemical reaction propagation rate as a function of pressure. Materials investigated have included CL-20, HMX, TATB, and RDX crystalline powders, LX-04, Comp B, and nitromethane. The anomalous correspondence between crystal structure, including in some instances isostructural phase transitions, on pressure-dependant RPRs of TATB, HMX, Nitromethane, CL-20, and PETN have been elucidated using micro-IR and -Raman spectroscopies. Here we specifically highlight pressure-dependent physicochemical mechanisms affecting the deflagration rate of nitromethane and epsilon-CL-20. We find that pressure induced splitting of symmetric stretch NO{sub 2} vibrations can signal the onset of increasingly more rapid combustion reactions

Ultrafast high strain rate acoustic wave measurements at high static pressure in a diamond anvil cell

We have used sub-picosecond laser pulses to launch ultra-high strain rate ({approx} 10{sup 9} s{sup -1}) nonlinear acoustic waves into a 4:1 methanol-ethanol pressure medium which has been precompressed in a standard diamond anvil cell. Using ultrafast interferometry, we have characterized acoustic wave propagation into the pressure medium at static compression up to 24 GPa. We find that the velocity is dependent on the incident laser fluence, demonstrating a nonlinear acoustic response which may result in shock wave behavior. We compare our results with low strain, low strain-rate acoustic data. This technique provides controlled access to regions of thermodynamic phase space that are otherwise difficult to obtain

Observation of off-Hugoniot shocked states with ultrafast time resolution

We apply ultrafast single shot interferometry to determine the pressure and density of argon shocked from up to 7.8 GPa static initial pressure in a diamond anvil cell. This method enables the observation of thermodynamic states distinct from those observed in either single shock or isothermal compression experiments, and the observation of ultrafast dynamics in shocked materials. We also present a straightforward method for interpreting ultrafast shock wave data which determines the index of refraction at the shock front, and the particle and shock velocities for shock waves in transparent materials. Based on these methods, we observe shocked thermodynamic states between the room temperature isotherm of argon and the shock adiabat of cryogenic argon at final shock pressures up to 28 GPa