Magnetism In 3d Transition Metals at High Pressures

This research project examined the changes in electronic and magnetic properties of transition metals and oxides under applied pressures, focusing on complex relationship between magnetism and phase stability in these correlated electron systems. As part of this LDRD project, we developed new measurement techniques and adapted synchrotron-based electronic and magnetic measurements for use in the diamond anvil cell. We have performed state-of-the-art X-ray spectroscopy experiments at the dedicated high-pressure beamline HP-CAT (Sector 16 Advanced Photon Source, Argonne National Laboratory), maintained in collaboration with of University of Nevada, Las Vegas and Geophysical Laboratory of The Carnegie Institution of Washington. Using these advanced measurements, we determined the evolution of the magnetic order in the ferromagnetic 3d transition metals (Fe, Co and Ni) under pressure, and found that at high densities, 3d band broadening results in diminished long range magnetic coupling. Our experiments have allowed us to paint a unified picture of the effects of pressure on the evolution of magnetic spin in 3d electron systems. The technical and scientific advances made during this LDRD project have been reported at a number of scientific meetings and conferences, and have been submitted for publication in technical journals. Both the technical advances and the physical understanding of correlated systems derived from this LDRD are being applied to research on the 4f and 5f electron systems under pressure

A new molecular solid phase of carbon dioxide at high pressure and temperature

We report the discovery of a new high-pressure molecular phase of carbon dioxide. The new polymorph, CO{sub 2} -IV, is formed by heating the high-pressure orthorhombic phase III to temperatures above 1000K at pressures between 12 and 33GPa. Analysis of the Raman spectrum of the new phase suggests a structure lacking inversion symmetry

Six-fold Coordinated Carbon Dioxide VI

Under standard conditions, carbon dioxide (CO{sub 2}) is a simple molecular gas and an important atmospheric constituent while silicon dioxide (SiO{sub 2}) is a covalent solid, and represents one of the fundamental minerals of the planet. The remarkable dissimilarity between these two group IV oxides is diminished at higher pressures and temperatures as CO{sub 2} transforms to a series of solid phases, from simple molecular to a fully covalent extended-solid V, structurally analogous to SiO{sub 2} tridymite. Here, we present the discovery of a new extended-solid phase of carbon dioxide (CO{sub 2}): a six-fold coordinated stishovite-like phase VI, obtained by isothermal compression of associated CO{sub 2}-II above 50GPa at 530-650K. Together with the previously reported CO{sub 2}-V and a-carbonia, this new extended phase indicates a fundamental similarity between CO{sub 2}--a prototypical molecular solid, and SiO{sub 2}--one of Earth's fundamental building blocks. The phase diagram suggests a limited stability domain for molecular CO{sub 2}-I, and proposes that the conversion to extended-network solids above 40-50 GPa occurs via intermediate phases II, III, and IV. The crystal structure of phase VI suggests strong disorder along the caxis in stishovite-like P4{sub 2}/mnm, with carbon atoms manifesting an average six-fold coordination within the framework of sp{sup 3} hybridization

Optical Response of Solid CO2_2 as a Tool for the Determination of the High Pressure Phase

We report first-principles calculations of the frequency dependent linear and second-order optical properties of the two probable extended-solid phases of CO$_2$--V, i.e. $I\bar42d$ and $P2_12_12_1$. Compared to the parent $Cmca$ phase the linear optical susceptibility of both phases is much smaller. We find that $I\bar42d$ and $P2_12_12_1$ differ substantially in their linear optical response in the higher energy regime. The nonlinear optical responses of the two possible crystal structures differ by roughly a factor of five. Since the differences in the nonlinear optical spectra are pronounced in the low energy regime, i.e. below the band gap of diamond, measurements with the sample inside the diamond anvil cell are feasible. We therefore suggest optical experiments in comparison with our calculated data as a tool for the unambiguous identification of the high pressure phase of CO$_2$.Comment: 4 pages 2 fig

Pressure Induced Bonding Changes in Carbon Dioxide: Six Fold Coordinated CO2

In this LDRD, we examined in detail the pressure-induced bonding and local coordination changes leading to the molecular {yields} associated {yields} extended-solid transitions in carbon dioxide (CO{sub 2}). We studied the progressive delocalization of electrons from the C=O molecular double bond at high pressures and temperatures, and determined the phase stability and physical properties of a new extended-solid CO{sub 2} phase (VI). We find that the new CO{sub 2} phase VI is based on a network of six-fold coordinated (octahedral) CO{sub 6} structures similar to the ultra-hard SiO{sub 2} phase stishovite

Electronic Transitions in f-electron Metals at High Pressures:

This study was to investigate unusual phase transitions driven by electron correlation effects that occur in many f-band transition metals and are often accompanied by large volume changes: {approx}20% at the {delta}-{alpha} transition in Pu and 5-15% for analogous transitions in Ce, Pr, and Gd. The exact nature of these transitions has not been well understood, including the short-range correlation effects themselves, their relation to long-range crystalline order, the possible existence of remnants of the transitions in the liquid, the role of magnetic moments and order, the critical behavior, and dynamics of the transitions, among other issues. Many of these questions represent forefront physics challenges central to Stockpile materials and are also important in understanding the high-pressure behavior of other f- and d-band transition metal compounds including 3d-magnetic transition monoxide (TMO, TM=Mn, Fe, Co, Ni). The overarching goal of this study was, therefore, to understand the relationships between crystal structure and electronic structure of transition metals at high pressures, by using the nation's brightest third-generation synchrotron x-ray at the Advanced Photon Source (APS). Significant progresses have been made, including new discoveries of the Mott transition in MnO at 105 GPa and Kondo-like 4f-electron dehybridization and new developments of high-pressure resonance inelastic x-ray spectroscopy and x-ray emission spectroscopy. These scientific discoveries and technology developments provide new insights and enabling tools to understand scientific challenges in stockpile materials. The project has broader impacts in training two SEGRF graduate students and developing an university collaboration (funded through SSAAP)

Electronic Spin Crossover of Iron in Ferroperclase in Earth?s Lower Mantle

Pressure-induced electronic spin-pairing transitions of iron and associated effects on the physical properties have been reported to occur in the lower-mantle ferropericlase, silicate perosvkite, and perhaps in post silicate perovskite at high pressures and room temperature. These recent results are motivating geophysicists and geodynamicists to reevaluate the implications of spin transitions on the seismic heterogeneity, composition, as well as the stability of the thermal upwellings of the Earth's lower mantle. Here we have measured the spin states of iron in ferropericlase and its crystal structure up to 95 GPa and 2000 K using a newly constructed X-ray emission spectroscopy and diffraction with the laser-heated diamond cell. Our results show that an isosymmetric spin crossover occurs over a pressure-temperature range extending from the upper part to the lower part of the lower mantle, and low-spin ferropericlase likely exists in the lowermost mantle. Although continuous changes in physical and chemical properties are expected to occur across the spin crossover, the spin crossover results in peculiar behavior in the thermal compression and sound velocities. Therefore, knowledge of the fraction of the spin states in the lower-mantle phases is thus essential to correctly evaluate the composition, geophysics, and dynamics of the Earth's lower mantle

High Pressure Materials Research using Advanced Third-Generation Synchrotron X-ray

The recent discoveries of nonmolecular phases of simple molecular solids [1,2] demonstrate the proof-of-the-principles for producing exotic phases by application of high pressure. Modern advances in theoretical and computational methodologies now make possible to explain or even predict novel structures and properties in a relatively wide range of length scales on the basis of thermodynamic stability [3]. Equally important in materials research is the recent developments in advanced x-ray and laser diagnostics that enable in-situ observations at the formidable pressure-temperature conditions [4]. Having benefited by all these developments, we discuss the first principle of the pressure-induced chemistry, 'Mbar Chemistry', with a few examples that may have important implications in materials research

Formation of the -N(NO)N(NO)- polymer at high pressure and stabilization at ambient conditions

A number of exotic structures have been formed through high-pressure chemistry, but applications have been hindered by difficulties in recovering the high-pressure phase to ambient conditions (i.e., one atmosphere and 300 K). Here we use dispersion-corrected density functional theory [PBE-ulg (Perdew-Burke-Ernzerhof flavor of DFT with the universal low gradient correction for long range London dispersion)] to predict that above 60 gigapascal (GPa) the most stable form of N(2)O (the laughing gas in its molecular form) is a one-dimensional polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03∼0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions, both polymers relax below 14 GPa to the same stable nonplanar trans-polymer. The predicted phonon spectrum and dissociation kinetics validates the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a type of conducting nonlinear optical polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions (very high pressure or temperature)

Synthesis of Non-molecular Nitrogen Phases at Mbar Pressures by Direct Laser-heating

Direct laser heating of molecular N2 to above 1400 K at 120-130 GPa results in the formation of a reddish amorphous phase and a transparent crystalline solid above 2000 K. Raman and x-ray data confirm that the transparent phase is cubic-gauche nitrogen (cg-N), while the reddish color of the amorphous phase might indicate the presence of N=N dish bonds. The quenched amorphous phase is stable down to at least 70GPa, analogous to cg-N, and could be a new non-molecular phase or an extension of the already known {eta}-phase. A chemo-physical phase diagram is presented which emphasizes the difference between pressure- and temperature-induced transitions from molecular to non-molecular solids, as found in other low Z systems