Inelastic x-ray scattering of dense solid oxygen: Evidence for intermolecular bonding

Meng, Yue; Eng, Peter J.; Tse, John S.; Shaw, Dawn M.; Hu, Michael Y.; Shu, Jinfu; Gramsch, Stephen A.; Kao, C.‐C.; Hemley, Russell J.; Mao, Ho‐kwang

doi:10.1073/pnas.0805601105

Cited by 54 publications

(40 citation statements)

References 38 publications

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“…The clusters (O 2 ) 4 are of particular importance for the oxygen solid state at extremely high pressure. 37,38 The giant clusters (O 2 ) N with several thousands of O 2 molecular units are potentially important for future technologies based on a relatively new concept called "chemistry with a hammer." 34,39,40 A polymeric form of oxygen (θ-O 4 phase based on a polymeric chain structural motif) was predicted in ref 41 on the basis of DFT calculations.…”

Section: Introductionmentioning

confidence: 99%

Structure, Energy, and Vibrational Frequencies of Oxygen Allotropes O_n (n ≤ 6) in the Covalently Bound and van der Waals Forms: Ab Initio Study at the CCSD(T) Level

Gadzhiev

Ignatov

Куликов

et al. 2012

J. Chem. Theory Comput.

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Recent experiments on the UV and electron beam irradiation of solid O 2 reveals a series of IR features near the valence antisymmetric vibration band of O 3 which are frequently interpreted as the formation of unusual O n allotropes in the forms of weak complexes or covalently bound molecules. In order to elucidate the question of the nature of the irradiation products, the structure, relative energies, and vibrational frequencies of various forms of O n (n = 1−6) in the singlet, triplet, and, in some cases, quintet states were studied using the CCSD(T) method up to the CCSD(T,full)/cc-pCVTZ and CCSD(T,FC)/aug-cc-pVTZ levels. The results of calculations demonstrate the existence of stable highly symmetric structures O 4 (D 3h ), O 4 (D 2d ), and O 6 (D 3d ) as well as the intermolecular complexes O 2 ·O 2 , O 2 ·O 3 , and O 3 ·O 3 in different conformations. The calculations show that the local minimum corresponding to the O 3 ···O complex is quite shallow and cannot explain the ν 3 band features close to 1040 cm −1 , as was proposed previously. For the ozone dimer, a new conformer was found which is more stable than the structure known to date. The effect of the ozone dimer on the registered IR spectra is discussed.

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Section: Introductionmentioning

confidence: 99%

Structure, Energy, and Vibrational Frequencies of Oxygen Allotropes O_n (n ≤ 6) in the Covalently Bound and van der Waals Forms: Ab Initio Study at the CCSD(T) Level

Gadzhiev

Ignatov

Куликов

et al. 2012

J. Chem. Theory Comput.

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“…Intermolecular interactions dictate the rich HP polymorphism [460] of solid oxygen. HP IXS of oxygen K-edge excitations to 38 GPa shows that O2 molecules interact predominantly through the half-filled 1πg* orbital <10 GPa [461]. Enhanced intermolecular interactions develop because of increasing overlap of the 1πg* orbital in the low-pressure phases, leading to electron delocalization and ultimately intermolecular bonding between O2 molecules at the transition to the ε-phase.…”

Section: Phase Transitionsmentioning

confidence: 99%

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

2016

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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.

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“…Under a higher pressure of approximately 8 GPa, the magnetic order of oxygen is destroyed, which leads to the ε-O 8 phase consisting of O 8 clusters (9, 10). The ε-O 8 phase displays the bonding characteristics of a closedshell system, in which the intermolecular interactions primarily involve the half-filled 1π g Ã orbital of O 2 (11). Above 96 GPa, ε-O 8 has been observed to transform into a metallic ζ-phase (12,13) and intriguingly exhibits superconductivity with a transition temperature of 0.6 K (14).…”

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confidence: 99%

Spiral chain O ₄ form of dense oxygen

Zhu

Wang

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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Oxygen is in many ways a unique element: It is the only known diatomic molecular magnet, and it exhibits an unusual O 8 cluster in its high-pressure solid phase. Pressure-induced molecular dissociation as one of the fundamental problems in physical sciences has been reported from theoretical or experimental studies of diatomic solids H 2 , N 2 , F 2 , Cl 2 , Br 2 , and I 2 but remains elusive for molecular oxygen. We report here the prediction of the dissociation of molecular oxygen into a polymeric spiral chain O 4 structure (space group I4 1 ∕acd, θ-O 4 ) above 1.92-TPa pressure using the particleswarm search method. The θ-O 4 phase has a similar structure as the high-pressure phase III of sulfur. The molecular bonding in the insulating ε-O 8 phase or the isostructural superconducting ζ-O 8 phase remains remarkably stable over a large pressure range of 0.008-1.92 TPa. The pressure-induced softening of a transverse acoustic phonon mode at the zone boundary V point of O 8 phase might be the ultimate driving force for the formation of θ-O 4 . Stabilization of θ-O 4 turns oxygen from a superconductor into an insulator by opening a wide band gap (approximately 5.9 eV) that originates from the sp 3 -like hybridized orbitals of oxygen and the localization of valence electrons.solid oxygen | spiral chain structure A s a long-standing problem in physics and chemistry, as well as earth and planetary sciences, high-pressure dissociation of diatomic molecules, such as H 2 , N 2 , O 2 , F 2 , Cl 2 , Br 2 , and I 2 , has attracted a lot of attention. Among these molecular systems, solid oxygen is a system of particular interest and exhibits many unusual physical properties by virtue of its molecular spin and the resultant spin-spin interactions, which make the system a critical test case for condensed-matter theory (1, 2). Oxygen is also the third most abundant element in the Solar System, and its behavior under extreme pressures provides important insight into the oxygen-related systems for a better understanding of the physics and chemistry of planetary interiors.Oxygen exhibits a rich polymorphism with seven unambiguously established crystalline phases. Upon cooling at ambient pressure, oxygen is in turn solidified to the paramagnetic γ-phase, the magnetically disordered (short-range ordered) β-phase (3, 4), and ultimately the antiferromagnetic α-phase (5). Upon compressing to approximately 6 GPa, the α-phase transforms into the antiferromagnetic δ-phase (6-8). Under a higher pressure of approximately 8 GPa, the magnetic order of oxygen is destroyed, which leads to the ε-O 8 phase consisting of O 8 clusters (9, 10). The ε-O 8 phase displays the bonding characteristics of a closedshell system, in which the intermolecular interactions primarily involve the half-filled 1π g Ã orbital of O 2 (11). Above 96 GPa, ε-O 8 has been observed to transform into a metallic ζ-phase (12, 13) and intriguingly exhibits superconductivity with a transition temperature of 0.6 K (14). This superconducting ζ-phase has been predicted by theory ...

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Inelastic x-ray scattering of dense solid oxygen: Evidence for intermolecular bonding

Cited by 54 publications

References 38 publications

Structure, Energy, and Vibrational Frequencies of Oxygen Allotropes O_n (n ≤ 6) in the Covalently Bound and van der Waals Forms: Ab Initio Study at the CCSD(T) Level

Structure, Energy, and Vibrational Frequencies of Oxygen Allotropes O_n (n ≤ 6) in the Covalently Bound and van der Waals Forms: Ab Initio Study at the CCSD(T) Level

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

Spiral chain O ₄ form of dense oxygen

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Inelastic x-ray scattering of dense solid oxygen: Evidence for intermolecular bonding

Cited by 54 publications

References 38 publications

Structure, Energy, and Vibrational Frequencies of Oxygen Allotropes On (n ≤ 6) in the Covalently Bound and van der Waals Forms: Ab Initio Study at the CCSD(T) Level

Structure, Energy, and Vibrational Frequencies of Oxygen Allotropes On (n ≤ 6) in the Covalently Bound and van der Waals Forms: Ab Initio Study at the CCSD(T) Level

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

Spiral chain O 4 form of dense oxygen

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Product

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About

Structure, Energy, and Vibrational Frequencies of Oxygen Allotropes O_n (n ≤ 6) in the Covalently Bound and van der Waals Forms: Ab Initio Study at the CCSD(T) Level

Structure, Energy, and Vibrational Frequencies of Oxygen Allotropes O_n (n ≤ 6) in the Covalently Bound and van der Waals Forms: Ab Initio Study at the CCSD(T) Level

Spiral chain O ₄ form of dense oxygen