Electronic structure and bonding in crystalline peroxides

Königstein, Markus; Sokol, A. A.; Catlow, C. Richard A.

doi:10.1103/physrevb.60.4594

Cited by 19 publications

(18 citation statements)

References 45 publications

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“…A detailed analysis of the peroxy species, which is isoelectronic with the F 2 molecule, and its role in solid oxides can be found for example in Ref. [27].…”

Section: Resultsmentioning

confidence: 99%

Oxygen interstitial structures in close-packed metal oxides

Sokol

Walsh

Catlow

2010

Chemical Physics Letters

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“…A detailed analysis of the peroxy species, which is isoelectronic with the F 2 molecule, and its role in solid oxides can be found for example in Ref. [27].…”

Section: Resultsmentioning

confidence: 99%

Oxygen interstitial structures in close-packed metal oxides

Sokol

Walsh

Catlow

2010

Chemical Physics Letters

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“…Early X-ray diffraction (XRD) experiments assigned a tetragonal 'calcium carbide' structure of space group I4/mmm to CaO 2 [4]. This same structure was already known to be formed by heavier alkaline earth metal peroxides [5,6]. Recently, Zhao et al [7] used an adaptive genetic algorithm and density functional theory (DFT) calculations to search for structures of CaO 2 , finding a new orthorhombic ground state structure of P na2 1 symmetry, which is calculated to be close to thermodynamic stability at zero pressure and temperature.…”

Section: Introductionmentioning

confidence: 94%

Calcium peroxide from ambient to high pressures

Nelson

Needs

Pickard

2015

Phys. Chem. Chem. Phys.

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Structures of calcium peroxide (CaO2) are investigated in the pressure range 0-200 GPa using the ab initio random structure searching (AIRSS) method and density functional theory (DFT) calculations. At 0 GPa, there are several CaO2 structures very close in enthalpy, with the ground-state structure dependent on the choice of exchange-correlation functional. Further stable structures for CaO2 with C2/c, I4/mcm and P21/c symmetries emerge at pressures below 40 GPa. These phases are thermodynamically stable against decomposition into CaO and O2. The stability of CaO2 with respect to decomposition increases with pressure, with peak stability occurring at the CaO B1-B2 phase transition at 65 GPa. Phonon calculations using the quasiharmonic approximation show that CaO2 is a stable oxide of calcium at mantle temperatures and pressures, highlighting a possible role for CaO2 in planetary geochemistry. We sketch the phase diagram for CaO2, and find at least five new stable phases in the pressure-temperature ranges 0 ≤ P ≤ 60 GPa, 0 ≤ T ≤ 600 K, including two new candidates for the zero-pressure ground state structure.

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“…[16]. In the three-dimensional solid MO, M ¼ Ca À Ba, most of the d character remains in empty conduction bands [17]. In the nearest neighbor of Ba, metallic cesium, the high-pressure isostructural phase transformation at about 4.3 GPa is attributed to a transition from a predominant s bonding orbital to a predominant d bonding orbital; for the latest summary, see Ref.…”

Section: The Hybridization Of Ca-bamentioning

confidence: 99%

Cesium and barium as honorary d elements: CsN 7 Ba as an example

Gagliardi¹,

Pyykkö

2003

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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Abstract. Quantum chemical calculations suggest that inverse sandwich compounds with the general formula MN 7 M 0 , where M is an alkali metal (K,Rb,Cs), N 7 is a ten-p-electron ring, and M 0 is an alkaline-earth metal (Ca,Sr,Ba), are local C 7v minima. Among these systems, the CsN 7 Ba molecule is the stablest of all and presents a barrier of 35 kcal/mol to dissociation towards CsNBa and three N 2 molecules. Substantial 5d character is found in the bonding. Possible ways of making these high-energy compounds are discussed.

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Electronic structure and bonding in crystalline peroxides

Cited by 19 publications

References 45 publications

Oxygen interstitial structures in close-packed metal oxides

Oxygen interstitial structures in close-packed metal oxides

Calcium peroxide from ambient to high pressures

Cesium and barium as honorary d elements: CsN 7 Ba as an example

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