The<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mi>ε</mml:mi></mml:math>Phase of Solid Oxygen: Evidence of an<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi>O</mml:mi></mml:mrow><mml:mrow><mml:mn>4</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>Molecule Lattice

Gorelli, Federico A.; Ulivi, Lorenzo; Santoro, Mario; Bini, Roberto

doi:10.1103/physrevlett.83.4093

Cited by 149 publications

(97 citation statements)

References 22 publications

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“…Fluid O 2 exists to 5.5 GPa and solidifies upon further compression, forming the rombohedral ␤-phase (1) at 5.5 GPa, the orthorhmbic ␦-phase (2) at 9.6 GPa, the monoclinic -phase (3, 4) at 10 GPa, and the modified monoclinic -phase (5) at 96 GPa. These transformations are accompanied by marked changes in color, density, and vibrational dynamics (6)(7)(8)(9), and by metallization (10), including the appearance of superconductivity at low temperatures (11). These remarkable phenomena in condensed oxygen are consequences of pressure-induced changes in electronic structure and bonding, an area of fundamental importance but previously inaccessible by in situ high-pressure studies.…”

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confidence: 99%

“…These remarkable phenomena in condensed oxygen are consequences of pressure-induced changes in electronic structure and bonding, an area of fundamental importance but previously inaccessible by in situ high-pressure studies. Raman and infrared observations of the -phase, specifically the anomaly in the intramolecular vibrational frequencies of O 2 (6,8) and the appearance of strong infrared absorption (7,8), have led to suggestions of increased intermolecular interaction, electronic charge transfer, and a paired O 2 model for the -phase. The tendency toward association of O 2 molecules in the -phase was also proposed based on results of early density functional calculations (12).…”

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confidence: 99%

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

Meng

Eng

Tse

et al. 2008

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

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The detailing of the intermolecular interactions in dense solid oxygen is essential for an understanding of the rich polymorphism and remarkable properties of this element at high pressure. Synchrotron inelastic x-ray scattering measurements of oxygen K-edge excitations to 38 GPa reveal changes in electronic structure and bonding on compression of the molecular solid. The measurements show that O 2 molecules interact predominantly through the half-filled 1π g * orbital <10 GPa. Enhanced intermolecular interactions develop because of increasing overlap of the 1π g * orbital in the low-pressure phases, leading to electron delocalization and ultimately intermolecular bonding between O 2 molecules at the transition to the ε-phase. The ε-phase, which consists of (O 2 ) 4 clusters, displays the bonding characteristics of a closed-shell system. Increasing interactions between (O 2 ) 4 clusters develop upon compression of the ε-phase, and provide a potential mechanism for intercluster bonding in still higher-pressure phases.

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confidence: 99%

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confidence: 99%

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

Meng

Eng

Tse

et al. 2008

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

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“…Active space CAS (16,14) for O 6 does not converge correctly to dissociation limit O 6 → 2O 3 . We suppose that the full valence active space CAS(24,18) is enough to describe the reaction path because it includes all (quasi)degenerate orbitals, and active space CAS (12,9) shows correct results for the ozone molecule.…”

Section: Journal Of Chemical Theory and Computationmentioning

confidence: 95%

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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“…IR spectra were measured using a Bruker IFS-120 HR Fourier transform infrared spectrometer equipped with an optical beam condenser based on ellipsoidal mirrors 36 . Raman spectra were performed using the 647.1-nm line of a Kr þ laser as the excitation source.…”

Section: Methodsmentioning

confidence: 99%

High-pressure synthesis of a polyethylene/zeolite nano-composite material

et al. 2013

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Meso/micro-porous solids, such as zeolites, are complex materials used in an impressive range of applications. Here we photo-polymerized ethylene using non-catalytic high-pressure techniques at 0.5-1.5 GPa under ultraviolet (351-364 nm) irradiation on a sub-nanometre scale in the channels of a pure SiO 2 zeolite, silicalite, to obtain a unique nano-composite material with drastically modified mechanical properties. The structure obtained contains single polyethylene chains, which adapt very well to the confining channels as shown by optical spectroscopy and X-ray diffraction. The formation of this nano-composite results in significant increases in bulk modulus and density, and the thermal expansion coefficient changes sign from negative to positive with respect to silicalite. Mechanical properties may thus be tuned by varying the amount of polymerized ethylene. Our findings could allow the high-pressure, catalyst-free synthesis of a unique generation of technological, functional materials based on simple hydrocarbons polymerized in confining meso/micro-porous solids.

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TheεPhase of Solid Oxygen: Evidence of anO4Molecule Lattice

Cited by 149 publications

References 22 publications

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

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

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 synthesis of a polyethylene/zeolite nano-composite material

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TheεPhase of Solid Oxygen: Evidence of anO4Molecule Lattice

Cited by 149 publications

References 22 publications

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

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

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 synthesis of a polyethylene/zeolite nano-composite material

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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