Minseob Kim

Two- and three-dimensional extended solids and metallization of compressed XeF2

The application of pressure, internal or external, transforms molecular solids into extended solids with more itinerant electrons to soften repulsive interatomic interactions in a tight space. Examples include insulator-to-metal transitions in O(2), Xe and I(2), as well as molecular-to-non-molecular transitions in CO(2) and N(2). Here, we present new discoveries of novel two- and three-dimensional extended non-molecular phases of solid XeF(2) and their metallization. At approximately 50 GPa, the transparent linear insulating XeF(2) transforms into a reddish two-dimensional graphite-like hexagonal layered structure of semiconducting XeF(4). Above 70 GPa, it further transforms into a black three-dimensional fluorite-like structure of the first observed metallic XeF(8) polyhedron. These simultaneously occurring molecular-to-non-molecular and insulator-to-metal transitions of XeF(2) arise from the pressure-induced delocalization of non-bonded lone-pair electrons to sp(3)d(2) hybridization in two-dimensional XeF(4) and to p(3)d(5) in three-dimensional XeF(8) through the chemical bonding of all eight valence electrons in Xe and, thereby, fulfilling the octet rule at high pressures.

Carbon Dioxide Carbonates in the Earth’s Mantle: Implications to the Deep Carbon Cycle

An increase in the ionic character in C-O bonds at high pressures and temperatures is shown by the chemical/phase transformation diagram of CO{sub 2}. The presence of carbonate carbon dioxide (i-CO{sub 2}) near the Earths core-mantle boundary condition provides insights into both the deep carbon cycle and the transport of atmospheric CO{sub 2} to anhydrous silicates in the mantle and iron core.

Highly repulsive interaction in novel inclusion D2–N2 compound at high pressure: Raman and x-ray evidence

We present spectral and structural evidences for the formation of a homogeneous cubic δ-N(2)-like, noncrystalline solid and an incommensuratelike hexagonal (P6(3)22) inclusion compound (N(2))(12)D(2), formed by compressing a nitrogen-rich mixture to 5.5 and 10 GPa, respectively. A strong repulsive coupling in (N(2))(12)D(2) is evident from a blue shift, discontinuous changes, and the absence of turnover of the D(2) vibron to 70 GPa--all in sharp contrast to both pure D(2) and other inclusion compounds. This repulsive interaction is responsible to the observed incommensuratelike structure and large internal pressure.

Superconductivity in highly disordered dense carbon disulfide

High pressure plays an increasingly important role in both understanding superconductivity and the development of new superconducting materials. New superconductors were found in metallic and metal oxide systems at high pressure. However, because of the filled close-shell configuration, the superconductivity in molecular systems has been limited to charge-transferred salts and metal-doped carbon species with relatively low superconducting transition temperatures. Here, we report the low-temperature superconducting phase observed in diamagnetic carbon disulfide under high pressure. The superconductivity arises from a highly disordered extended state (CS4 phase or phase III[CS4]) at ∼6.2 K over a broad pressure range from 50 to 172 GPa. Based on the X-ray scattering data, we suggest that the local structural change from a tetrahedral to an octahedral configuration is responsible for the observed superconductivity.

Phase diagram of carbon dioxide: update and challenges

We present the phase diagram of carbon dioxide with the most recent finding of coesite-like carbon dioxide, a missing analog to SiO2, address several controversies on phase VII and phase IV in terms of the phase metastabilities and thermal path-dependent phase transitions, and discuss the implications to the generalized phase diagram of simple molecular solids.

Time-resolved x-ray diffraction across water-ice-VI/VII transformations using the dynamic-DAC

We present recent time-resolved x-ray diffraction data obtained across the solidification of water to ice-VI and -VII at different compression rates. The structural evolution of ice-VI to ice-VII, however, is not a sharp transition, but occurs rather coarsely. The diffraction data shows an anisotropic compression behavior for ice VI; that is, the c-axis is more compressible than the a-axis at the same compression rate. Nevertheless, the present equations of state of both ice-VI and ice-VII obtained under dynamic loadings agree well with those previously obtained under static conditions. Hence, the present study demonstrates that time-resolved x-ray diffraction coupled with the dynamic-DAC is an effective method for investigating details of the structural response of materials over a wide range of well-controlled compression rates. Finally, we found the evidence for an X-ray induced chemical reaction of water and ice-VI. The impurities, produced by the x-ray induced chemical reaction, inhibit the formation of amorphous ice.

Pressure-induced phase and chemical transformations of lithium peroxide (Li2O2)

We present the pressure-induced phase/chemical changes of lithium peroxide (Li2O2) to 63 GPa using diamond anvil cells, confocal micro-Raman spectroscopy, and synchrotron x-ray diffraction. The Raman data show the emergence of the major vibrational peaks associated with O2 above 30 GPa, indicating the subsequent pressure-induced reversible chemical decomposition (disassociation) in dense Li2O2. The x-ray diffraction data of Li2O2, on the other hand, show no dramatic structural change but remain well within a P63/mmc structure to 63 GPa. Nevertheless, the Rietveld refinement indicates a subtle change in the structural order parameter z of the oxygen position O (13, 23, z) at around 35 GPa, which can be considered as a second-order, isostructural phase transition. The nearest oxygen-oxygen distance collapses from 1.56 Å at ambient condition to 1.48 Å at 63 GPa, resulting in a more ionic character of this layered crystal lattice, 3Li(+)+(LiO2)3 (3-). This structural change in turn advocates that Li2O2 decomposes to 2Li and O2, further augmented by the densification in specific molar volumes.

Phase Diagram and Transformations of Iron Pentacarbonyl to nm Layered Hematite and Carbon-Oxygen Polymer under Pressure.

We present the phase diagram of Fe(CO)5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO)5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K. The limited stability, in turn, signifies the temperature-induced weakening of Fe-CO back bonds, which eventually leads to the dissociation of Fe-CO at the onset of the polymerization of CO. The recovered polymer is a composite of novel nm-lamellar layers of crystalline hematite Fe2O3 and amorphous carbon-oxygen polymers. These results, therefore, demonstrate the synthesis of carbon-oxygen polymer by compressing Fe(CO)5, which advocates a novel synthetic route to develop atomistic composite materials by compressing organometallic compounds.

Transformation of hydrazinium azide to molecular N8 at 40 GPa

Hydrazinium azide (HA) has been investigated at high pressures to 68 GPa using confocal micro-Raman spectroscopy and synchrotron powder x-ray diffraction. The results show that HA undergoes structural phase transitions from solid HA-I to HA-II at 13 GPa, associated with the strengthening of hydrogen bonding, and then to N8 at 40 GPa. The transformation of HA to recently predicted N8 (N≡N+-N--N=N--N-+N≡N) is evident by the emergence of new peaks at 2384 cm-1, 1665 cm-1, and 1165 cm-1, arising from the terminal N≡N stretching, the central N=N stretching, and the N-N stretching, respectively. However, upon decompression, N8 decomposes to ε-N2 below 25 GPa, but the remnant can be seen as low as 3 GPa.

High energy density nitrogen-rich extended solids

Many simple molecules such as N2 and CO2 have the potential to form extended “polymeric” solids under extreme conditions, which can store a large sum of chemical energy in its three-dimensional network structures made of strong covalent bonds. Diatomic nitrogen is particularly of interest because of the uniquely large energy difference between the single (160 kJ/mol) and triple (950 kJ/mol) bonds. As such, the transformation of singly bonded polymeric nitrogen back to triply bonded diatomic nitrogen molecules can release large energy (~33 kJ/cm3 – three times that of HMX) without any negative environmental impact. Therefore, the goal of the present study has been to investigate the transformation of nitrogen and nitrogen-rich compounds to new singly bonded nitrogen-rich solids at high pressures and temperatures, using heated diamond anvil cells, Raman spectroscopy, and third-generation synchrotron x-ray diffraction. Recently, we have found a new form of singly bonded layered polymeric nitrogen (LP-N), syn...