Quantum and Classical Orientational Ordering in Solid Hydrogen

We present a unified view of orientational ordering in phases I, II, and III of solid hydrogen. Phases II and III are orientationally ordered, while the ordering objects in phase II are angular momenta of rotating molecules, and in phase III the molecules themselves. This concept provides quantitative explanation of the vibron softening, libron and roton spectra, and increase of the IR vibron oscillator strength in phase III. The temperature dependence of the effective charge parallels the frequency shifts of the IR and Raman vibrons. All three quantities are linear in the order parameter.Comment: Replaced with the final text, accepted for publication in PRL. 1 Fig. added. Misc. text revision

A molecular perspective on the limits of life: Enzymes under pressure

From a purely operational standpoint, the existence of microbes that can grow under extreme conditions, or "extremophiles", leads to the question of how the molecules making up these microbes can maintain both their structure and function. While microbes that live under extremes of temperature have been heavily studied, those that live under extremes of pressure have been neglected, in part due to the difficulty of collecting samples and performing experiments under the ambient conditions of the microbe. However, thermodynamic arguments imply that the effects of pressure might lead to different organismal solutions than from the effects of temperature. Observationally, some of these solutions might be in the condensed matter properties of the intracellular milieu in addition to genetic modifications of the macromolecules or repair mechanisms for the macromolecules. Here, the effects of pressure on enzymes, which are proteins essential for the growth and reproduction of an organism, and some adaptations against these effects are reviewed and amplified by the results from molecular dynamics simulations. The aim is to provide biological background for soft matter studies of these systems under pressure.Comment: 16 pages, 8 figure

High-Pressure Reentrant Ferroelectricity in PbTiO3_3 Revisited

We study ferroelectricity in the classic perovskite ferroelectric PbTiO$_3$ to very high pressures with density functional theory (DFT) and experimental diamond anvil techniques. We use second harmonic generation (SHG) spectroscopy to detect lack of inversion symmetry, if present. Consistent with early understanding and experiments, we find that ferroelectricity disappears at moderate pressures. However, the DFT calculations show that the disappearance arises from the overtaking of zone boundaries instabilities, and not to the squeezing out of the off-centering ferroelectric displacements with pressure, as previously thought. Our computations also predict a dramatic double reentrance of ferroelectricity at higher pressures, not yet seen in experiments

Doming Modes and Dynamics of Model Heme Compounds

Synchrotron far-IR spectroscopy and density-functional calculations are used to characterize the low-frequency dynamics of model heme FeCO compounds. The “doming” vibrational mode in which the iron atom moves out of the porphyrin plane while the periphery of this ring moves in the opposite direction determines the reactivity of oxygen with this type of molecule in biological systems. Calculations of frequencies and absorption intensities and the measured pressure dependence of vibrational modes in the model compounds are used to identify the doming and related normal modes

The Application of Micro-Raman Spectroscopy to Analysis and Identification of Minerals in Thin Section

Micro-Raman spectroscopy is a useful analytical tool for studying minerals in thin section. The advantages of this technique as a structural probe for analysis of micron-size minerals are demonstrated with a study of polymorphism of SiO2 and MgSiO3. Three polymorphs of silica, -quartz, coesite, and glass, in a thin section of Coconino sandstone were identified in situ with a Raman microprobe. The Raman spectra of these phases were compared to that measured for stishovite obtained from the same rock. Spectra of protoenstatite, orthoenstatite, and clinoenstatite, three polymorphs of MgSiO3, are consistent with their similar pyroxene chain structures but different space groups. The characteristic Raman spectra in each instance could be used for finger-printing identification of the phases and their orientations