Krypton and the Fundamental Flaw of the Lennard-Jones Potential.

We have performed a series of neutron scattering experiments on supercritical krypton. Our data and analysis allow us to characterize the Frenkel line crossover in this model monatomic fluid. The data from our measurements was analyzed using Empirical Potential Structure Refinement to determine the short- and medium-range structure of the fluids. We find evidence for several shells of neighbors which form approximately concentric rings of density about each atom. The ratio of second to first shell radius is significantly larger than in any crystal structure. Modeling krypton using a Lennard-Jones potential is shown to give significant errors, notably that the liquid is overstructured. The true potential appears to be longer ranged and with a softer core than the 6-12 powerlaws permit.

Characterization of the high-pressure and high-temperature phase diagram and equation of state of chromium.

The high-pressure and high-temperature phase diagram of chromium has been investigated both experimentally (in situ), using a laser-heated diamond-anvil cell technique coupled with synchrotron powder X-ray diffraction, and theoretically, using ab initio density-functional theory simulations. In the pressure-temperature range covered experimentally (up to 90 GPa and 4500 K, respectively) only the solid body-centred-cubic and liquid phases of chromium have been observed. Experiments and computer calculations give melting curves in agreement with each other that can both be described by the Simon-Glatzel equation [Formula: see text]. In addition, a quasi-hydrostatic equation of state at ambient temperature has been experimentally characterized up to 131 GPa and compared with the present simulations. Both methods give very similar third-order Birch-Murnaghan equations of state with bulk moduli of 182-185 GPa and respective pressure derivatives of 4.74-5.15. According to the present calculations, the obtained melting curve and equation of state are valid up to at least 815 GPa, at which pressure the melting temperature is 9310 K. Finally, from the obtained results, it was possible to determine a thermal equation of state of chromium valid up to 65 GPa and 2100 K.

Structural Markers of the Frenkel Line in the Proximity of Widom Lines.

We have performed a neutron scattering experiment on supercritical fluid nitrogen at 160 K (1.27 TC) over a wide pressure range (7.8 MPa/0.260 g/mL-125 MPa/0.805 g/mL). This has enabled us to study the process by which nitrogen changes from a fluid that exhibits gaslike behavior to one that exhibits rigid liquidlike behavior at a temperature close to, but above, the critical temperature by crossing the Widom lines followed by the Frenkel line on pressure (density) increase. We find that the Frenkel line transition is indicated by a transition to a regime of rigid liquidlike behavior in which the coordination number remains constant within error, in agreement with our previous work at 300 K. The Frenkel line transition takes place at approximately the same density at 160 and 300 K. The data do not conclusively show an additional transition at the location of the known Widom lines. We find that behavior remains gaslike until the Frenkel line is crossed and our data support the hypothesis that Widom line transitions are density increase-driven.

Observation of Liquid-Liquid Phase Transitions in Ethane at 300 K.

We have conducted Raman spectroscopy experiments on liquid ethane (C2H6) at 300 K, obtaining a large amount of data at very high resolution. This has enabled the observation of Raman peaks expected but not previously observed in liquid ethane and a detailed experimental study of the liquid that was not previously possible. We have observed a transition between rigid and nonrigid liquid states in liquid ethane at ca. 250 MPa corresponding to the recently proposed Frenkel line, a dynamic transition between rigid liquid (liquidlike) and nonrigid liquid (gaslike) states beginning in the subcritical region and extending to arbitrarily high pressure and temperature. The observation of this transition in liquid (subcritical) ethane allows a clear differentiation to be made between the Frenkel line (beginning in the subcritical region at higher density than the boiling line) and the Widom lines (emanating from the critical point and not existing in the subcritical region). Furthermore, we observe a narrow transition at ca. 1000 MPa to a second rigid liquid state. We propose that this corresponds to a state in which orientational order must exist to achieve the expected density and can view the transition in analogy to the transition in the solid state away from the orientationally disordered phase I to the orientationally ordered phases II and III.

High Pressure Raman, Optical Absorption, and Resistivity Study of SrCrO4.

We studied the electronic and vibrational properties of monazite-type SrCrO4 under compression. The study extended the pressure range of previous studies from 26 to 58 GPa. The existence of two previously reported phase transitions was confirmed at 9 and 14 GPa, and two new phase transitions were found at 35 and 48 GPa. These transitions involve several changes in the vibrational and transport properties with the new high-pressure phases having a conductivity lower than that of the previously known phases. No evidence of chemical decomposition or metallization of SrCrO4 was detected. A tentative explanation for the reported observations is discussed.

Determining molecular orientation via single molecule SERS in a plasmonic nano-gap.

In this work, plasmonic nano-gaps consisting of a silver nanoparticle coupled to an extended silver film have been fully optimized for single molecule Surface-Enhanced Raman Scattering (SERS) spectroscopy. The SERS signal was found to be strongly dependent on the particle size and the molecule orientation with respect to the field inside the nano-gap. Using Finite Difference Time Domain (FDTD) simulations to complement the experimental measurements, the complex interplay between the excitation enhancement and the emission enhancement of the system as a function of particle size were highlighted. Additionally, in conjunction with Density Functional Theory (DFT), the well-defined field direction in the nano-gap enables to recover the orientation of individual molecules.

Hydrogenation of Graphene by Reaction at High Pressure and High Temperature.

The chemical reaction between hydrogen and purely sp(2)-bonded graphene to form graphene's purely sp(3)-bonded analogue, graphane, potentially allows the synthesis of a much wider variety of novel two-dimensional materials by opening a pathway to the application of conventional chemistry methods in graphene. Graphene is currently hydrogenated by exposure to atomic hydrogen in a vacuum, but these methods have not yielded a complete conversion of graphene to graphane, even with graphene exposed to hydrogen on both sides of the lattice. By heating graphene in molecular hydrogen under compression to modest high pressure in a diamond anvil cell (2.6-5.0 GPa), we are able to react graphene with hydrogen and propose a method whereby fully hydrogenated graphane may be synthesized for the first time.

Theoretical and Experimental Study of the Crystal Structures, Lattice Vibrations, and Band Structures of Monazite-Type PbCrO4, PbSeO4, SrCrO4, and SrSeO4.

The crystal structures, lattice vibrations, and electronic band structures of PbCrO4, PbSeO4, SrCrO4, and SrSeO4 were studied by ab initio calculations, Raman spectroscopy, X-ray diffraction, and optical-absorption measurements. Calculations properly describe the crystal structures of the four compounds, which are isomorphic to the monazite structure and were confirmed by X-ray diffraction. Information is also obtained on the Raman- and IR-active phonons, with all of the vibrational modes assigned. In addition, the band structures and electronic densities of states of the four compounds were determined. All are indirect-gap semiconductors. In particular, chromates are found to have band gaps smaller than 2.5 eV and selenates higher than 4.3 eV. In the chromates (selenates), the upper part of the valence band is dominated by O 2p states and the lower part of the conduction band is composed primarily of electronic states associated with the Cr 3d and O 2p (Se 4s and O 2p) states. Calculations also show that the band gap of PbCrO4 (PbSeO4) is smaller than the band gap of SrCrO4 (SrSeO4). This phenomenon is caused by Pb states, which, to some extent, also contribute to the top of the valence band and the bottom of the conduction band. The agreement between experiments and calculations is quite good; however, the band gaps are underestimated by calculations, with the exception of the bang gap of SrCrO4, for which theory and calculations agree. Calculations also provide predictions of the bulk modulus of the studied compounds.

High-pressure synthesis, amorphization, and decomposition of silane.

By compressing elemental silicon and hydrogen in a diamond anvil cell, we have synthesized polymeric silicon tetrahydride (SiH(4)) at 124 GPa and 300 K. In situ synchrotron x-ray diffraction reveals that the compound forms the insulating I4(1)/a structure previously proposed from ab initio calculations for the high-pressure phase of silane. From a series of high-pressure experiments at room and low temperature on silane itself, we find that its tetrahedral molecules break up, while silane undergoes pressure-induced amorphization at pressures above 60 GPa, recrystallizing at 90 GPa into the polymeric crystal structures.