Crystal Structure of Carbon Dioxide at High Pressure: “Superhard” Polymeric Carbon Dioxide

Yoo, Choong‐Shik; Cynn, Hyunchae; Gygi, François; Galli, Giulia; Iota, V.; Nicol, Malcolm; Carlson, Stefan; Häusermann, Daniel M.; Mailhiot, C.

doi:10.1103/physrevlett.83.5527

Cited by 227 publications

(247 citation statements)

References 20 publications

Supporting

Mentioning

226

Contrasting

Unclassified

Order By: Relevance

“…Their calculated value of the CO 2 tilt angle j of 52°was in exact agreement with the observed. Also, the DFT study by Bonev et al 34 ruled out the experimentally derived hypothesis 12 that phase III was a high-strength material with the bulk modulus of 87 GPa and was not a molecular crystal.…”

mentioning

confidence: 99%

“…Despite its abundance in the Earth's atmosphere and ubiquity in other planets and asteroids in its ice forms, there remain many gaps in our knowledge of the phase diagram of CO 2 2,10 . Today, intense experimental efforts are devoted to explore the high pressure-temperature range in which non-molecular phases [11][12][13][14][15][16][17][18][19] are observed. The phase diagram in the lower pressuretemperature range is relatively well characterized, yet some aspects of the phases there remain uncertain or unknown to this day.…”

mentioning

confidence: 99%

See 1 more Smart Citation

A solid–solid phase transition in carbon dioxide at high pressures and intermediate temperatures

Sode

Voth

et al. 2013

Nat Commun

View full text Add to dashboard Cite

Despite its terrestrial abundance and astrochemical significance, many aspects of the phase diagram of solid carbon dioxide remain uncertain or unknown. The observed transition pressures from cubic to orthorhombic phase range widely from 2.5 GPa at 80 K to above 18 GPa at room temperature. The vibrational Raman bands that appear at higher pressure and serve as a decisive proof of the existence of the orthorhombic phase have never been assigned. Here we introduce a general ab initio computational method that can predict the Gibbs free energies and thus phase diagrams of molecular crystals. Using this with secondorder Møller-Plesset perturbation theory, we obtain the transition pressure of 13 GPa at 0 K with small temperature dependence, which is in line with many experiments. We also computationally reproduce the vibrational Raman bands and explain the pressure dependence of the structure parameters and Raman band positions of both phases quantitatively.

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

A solid–solid phase transition in carbon dioxide at high pressures and intermediate temperatures

Sode

Voth

et al. 2013

Nat Commun

View full text Add to dashboard Cite

show abstract

“…It has been suggested that the extended phases of low-Z molecular solids made of interconnecting strong covalent bonds are an entirely new class of materials that may exhibit novel properties including super hardness, 33 optical nonlinearity, 34 superconductivity, 35 and high energy density. 36 The present study clearly demonstrates for the first time that such novel materials can be synthesized at high pressures and recovered to ambient conditions; that is, the high energy content of p-CO, rivaling or exceeding that of HMX.…”

Section: Novel Energetic Content Of P-comentioning

confidence: 99%

Pressure-Induced Polymerization of Carbon Monoxide: Disproportionation and Synthesis of an Energetic Lactonic Polymer

et al. 2006

Self Cite

View full text Add to dashboard Cite

We have studied pressure-induced chemical reactions in carbon monoxide using both a diamond-anvil cell and a modified large volume press. Our spectroscopic data reveal that carbon monoxide disproportionates into molecular CO 2 and a solid lactone-type polymer; photochemically above 3.2 GPa, thermochemically above 5 GPa at 300K, or at 3 GPa and ~2000K as achieved by laser heating. The solid product can be recovered at ambient conditions with a high degree of conversion, measured to be up to 95% of the original CO. Its fundamental chemical structure includes β-lactone and conjugated C=C, which can be considered a severely modified polymeric carbon suboxide with open ladders and smaller five-membered rings. The polymer is metastable at ambient conditions, spontaneously liberating CO 2 gases exothermically. We find that the recovered polymer has a high energy density, 1-8 KJ/g, and is very combustible. We estimate the density of recovered CO polymer to be at least 1.65 g/cm 3 .2

show abstract

“…Under HP, molecular CO is converted into an extended polymeric solid with very high energy density [436]. Dry ice CO2 becomes quartz-like and exhibits a rich phase diagram [437][438][439][440][441][442] [443] and pressure-induced amorphization [444,445]. With different arrangements of hydrogen bonding, H2O alone has fifteen stable phases and an additional fifteen distinctive metastable crystalline, amorphous, and fluid phases [97,267,394,396,[446][447][448][449][450][451][452][453][454][455][456][457][458][459].…”

Section: Phase Transitionsmentioning

confidence: 99%

High-pressure studies with x-rays using diamond anvil cells

2016

View full text Add to dashboard Cite

Pressure profoundly alters all states of matter. The symbiotic development of ultrahighpressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials' properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. These HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and magnetic properties of materials over a wide range of pressure-temperature conditions.

show abstract

Crystal Structure of Carbon Dioxide at High Pressure: “Superhard” Polymeric Carbon Dioxide

Cited by 227 publications

References 20 publications

A solid–solid phase transition in carbon dioxide at high pressures and intermediate temperatures

A solid–solid phase transition in carbon dioxide at high pressures and intermediate temperatures

Pressure-Induced Polymerization of Carbon Monoxide: Disproportionation and Synthesis of an Energetic Lactonic Polymer

High-pressure studies with x-rays using diamond anvil cells

Contact Info

Product

Resources

About