Spontaneous Dissociation of Xenon Tetroxide: Phase and Structural Changes

Slepkov, Vladimir A.; Kozlova, S. G.; Габуда, С. П.

doi:10.1021/jp2031658

Cited by 4 publications

(10 citation statements)

References 23 publications

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“…The paper by Slepkov et al 15 ). Thus, the structure of these dioxides was optimised and their electronic structure analysed herein.…”

Section: Resultsmentioning

confidence: 99%

“…basis set. 40 The explicit correlation space was made up of 22 electrons in 15 orbitals [CASSCF (22,15)] corresponding to all the valence p orbitals in Ng and O. The resulting multi-con gurational self-consistent eld wavefunction was correlated to second order under the CASPT2 formalism.…”

Section: Methodsmentioning

confidence: 99%

“…Its explosive character accounts for its high endothermicity 14 ( =+642 kJ mol − 1 ). Slepkov et al 15 Herein we address the nature of the chemical bond in three molecules RnO 4 , RnO 2 (η 2 -O 2 ) and Rn(η 2 -O 2 ) 2 none of which have ever been identi ed. We investigate their stability toward decomposition, and establish points of commonality and differences in the chemistry of xenon and radon, given that the oxides of the former are better studied.…”

Section: Introductionmentioning

confidence: 99%

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The inert pair effect on the heavy noble gases: New insights from radon tetroxide.

Bandeira¹,

Marçalo

2022

Preprint

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A quantum chemical survey of radon and xenon tetroxides (NgO4, Ng = Xe,Rn) is reported herein. The intermediate species that will form in their explosive decomposition back to their elemental states (Ng and O2) were also studied and their energetics compared. While Td symmetric RnO4 is a minimum energy structure, its standard enthalpy of formation is 88.6 kJ mol− 1 higher than for XeO4. The reason for this higher instability lies in what is known as the inert pair effect. This work adds to what is established wisdom in inorganic chemistry textbooks, a feature of the heavy elements of groups 13–15, extending it to include group 18.

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“…The paper by Slepkov et al 15 ). Thus, the structure of these dioxides was optimised and their electronic structure analysed herein.…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The inert pair effect on the heavy noble gases: New insights from radon tetroxide.

Bandeira¹,

Marçalo

2022

Preprint

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“…Recently, Slepkov et al 39. suggested that the D 2 h isomer of XeO 4 may be an intermediate in the spontaneous dissociation of XeO 4 during its transition from the solid phase to the liquid phase.…”

Section: Resultsmentioning

confidence: 99%

Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃

Vent‐Schmidt

Goettel

Schrobilgen

et al. 2015

Chemistry A European J

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The photolytic behavior of the thermochemically unstable xenon(VIII) oxide XeO4 was investigated by UV irradiation in noble-gas and F2 matrices. Photolysis of Xe(16) O4 or Xe(18) O4 in noble-gas matrices at 365 nm yielded XeO3 and a new xenon(VIII) oxide, namely, (η(2) -O2 )XeO3 , which, along with XeO4 , was characterized by matrix-isolation IR spectroscopy and quantum-chemical calculations. Calculations of the UV spectrum showed that the photodecomposition is induced by an n→σ* transition, but the nature of the excitation differs when different light sources are used. There is strong evidence for the formation of mobile (1) D excited O atoms in the case of excitation at 365 nm, which led to the formation of (η(2) -O2 )XeO3 by reaction with XeO4 . Matrix-isolation IR spectroscopy in Ne and Ar matrices afforded the natural-abundance xenon isotopic pattern for the ν3 (T2 ) stretching mode of Xe(16) O4 , and (18) O enrichment provided the (16) O/(18) O isotopic shifts of XeO4 and (η(2) -O2 )XeO3 .

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“…The potential energy surfaces corresponding to dissociation to Xe and O 2 were studied in an attempt to better understand the instability of XeO 4 . 38 It was proposed that the spontaneous explosion of XeO 4 is caused by a transition from T d to D 2h point symmetry which is triggered by rearrangement of electronic levels due to a Jahn-Teller effect. There is, however, no experimental evidence that XeO 4 undergoes a change in its molecular symmetry; in fact, T d symmetry has been documented for XeO 4 in HF, CH 3 CN, and BrF 5 solvents 39 as well as in the solid state 7 and in the gas phase.…”

Section: Theoretical Treatment Of Noble-gas Compoundsmentioning

confidence: 99%

Noble gases

Schrobilgen

Brock

2012

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This Chapter provides a digest of the literature reported during 2011 concerning the noble-gases with emphases placed on the syntheses, isolation, and characterisations of new noble-gas compounds. Its intent is to highlight discovery and provide insight into current research trends in the field of noble-gas chemistry. HighlightsHighlights include: the syntheses and characterisations of the mixed Xe II /Xe IV complexes a-XeOF 4 ÁXeF 2 and b-XeOF 4 ÁXeF 2 ; and XeO 2 , the missing oxide of xenon.An entertaining and informative book has recently been published which vividly describes the history of the discovery the noble gases, their properties, and uses from the perspective of the author, a geophysicist, who has worked with the noble gases for ca. 50 years. 1 However, the book is a disappointment to the chemist in that the rich chemistry associated with the noble-gases has been ignored and denied as we approach the 50th anniversary of the discovery of noble-gas reactivity (March 23, 1962). In his book, David E. Fisher states: (1) ' '[This] is the story of the discovery and uses of the noble gases, a group of elements vanishingly rare on our planet which in fact do nothing.'' and (2) ''Á Á Áthe noble gases, which don't do anything, which don't react either chemically or biologicallyÁ Á Á''. As is apparent from the present and prior Annual Reports, this, fortunately, is not the case. An excellent review of this book has recently appeared and should be consulted. 2 Syntheses of new noble-gas compoundsThe interaction of XeF 2 with excess XeOF 4 resulted in the mixed oxidation state complexes, a-XeOF 4 ÁXeF 2 and b-XeOF 4 ÁXeF 2 . 3 The more stable a-phase was characterized by X-ray crystallography and showed that the XeF 2 molecules are symmetrically coordinated through their F ligands to the Xe(VI) atoms of the XeOF 4 molecules which are, in turn, coordinated to four XeF 2 molecules (Fig. 1). A second, high-temperature phase, b-XeOF 4 ÁXeF 2 , was identified in admixture with a-XeOF 4 Á

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Spontaneous Dissociation of Xenon Tetroxide: Phase and Structural Changes

Cited by 4 publications

References 23 publications

The inert pair effect on the heavy noble gases: New insights from radon tetroxide.

The inert pair effect on the heavy noble gases: New insights from radon tetroxide.

Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃

Noble gases

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Spontaneous Dissociation of Xenon Tetroxide: Phase and Structural Changes

Cited by 4 publications

References 23 publications

The inert pair effect on the heavy noble gases: New insights from radon tetroxide.

The inert pair effect on the heavy noble gases: New insights from radon tetroxide.

Ultraviolet Photolysis Studies on XeO4 in Noble‐Gas and F2 Matrices and the Formation and Characterization of a New XeVIII Oxide, (η2‐O2)XeO3

Noble gases

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Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃