Caesium sesquioxide explained

Caesium sesquioxide is a chemical compound with the formula or more accurately . It is an oxide of caesium containing oxygen in different oxidation states. It consists of caesium cations, superoxide anions and peroxide anions . Caesium in this compound has an oxidation state of +1, while oxygen in superoxide has an oxidation state of −1/2 and oxygen in peroxide has an oxidation state of −1. This compound has a structural formula of .[1] [2] Compared to the other caesium oxides, this phase is less well studied,[3] but has been long present in the literature.[4] It can be created by thermal decomposition of caesium superoxide at 290 °C.[5]

The compound is often studied as an example of a Verwey type charge ordering transition at low temperatures.[6] [7] [8] There were some theoretical suggestions that would be a ferromagnetic half metal,[9] but along with the closely related rubidium sesquioxide, experimental results found a magnetically frustrated system. Below about 200 K, the structure changes to tetragonal symmetry.[10] Electron paramagnetic resonance and nuclear magnetic resonance measurements show a complicated low temperature magnetic behavior that depends on the orientation of the oxygen dimers and superexchange through the caesium atoms.[11]

Notes and References

  1. Winterlik . Jürgen . Fecher . Gerhard H. . Jenkins . Catherine A. . Medvedev . Sergey . Felser . Claudia . Kübler . Jürgen . Mühle . Claus . Doll . Klaus . Jansen . Martin . Palasyuk . Taras . Trojan . Ivan . Eremets . Mikhail I. . Emmerling . Franziska . 5. Exotic magnetism in the alkali sesquioxides Rb4O6 and Cs4O6 . Physical Review B . 79 . 21 . 2009-06-09 . 1098-0121 . 10.1103/physrevb.79.214410 . 214410. 0904.4338. 2009PhRvB..79u4410W . 118706339.
  2. Web site: Chempendix - Oxidation States .
  3. Band . A. . Albu-Yaron . A. . Livneh . T. . Cohen . H. . Feldman . Y. . Shimon . L. . Popovitz-Biro . R. . Lyahovitskaya . V. . Tenne . R. . Characterization of Oxides of Cesium . The Journal of Physical Chemistry B . American Chemical Society (ACS) . 108 . 33 . 2004-07-27 . 1520-6106 . 10.1021/jp036432o . 12360–12367.
  4. Helms . Alfred . Klemm . Wilhelm . Über die Kristallstrukturen der Rubidium- und Cäsiumsesquioxyde . Zeitschrift für anorganische und allgemeine Chemie . Wiley . 242 . 2 . 1939-08-29 . 0863-1786 . 10.1002/zaac.19392420210 . 201–214. de.
  5. Merz . Patrick . Schmidt . Marcus . Felser . Claudia . Jansen . Martin . Thermo-analytical Investigations on the Superoxides AO2 (A = K, Rb, Cs), Revealing Facile Access to Sesquioxides A4O6 . Zeitschrift für anorganische und allgemeine Chemie . Wiley . 643 . 8 . 2017-03-24 . 0044-2313 . 10.1002/zaac.201700013 . 544–547.
  6. Web site: Max Planck Society . Charge order and electron localization in a molecule-based solid . Phys.org . 2018-01-19 . 2021-11-26.
  7. Adler . Peter . Jeglič . Peter . Reehuis . Manfred . Geiß . Matthias . Merz . Patrick . Knaflič . Tilen . Komelj . Matej . Hoser . Andreas . Sans . Annette . Janek . Jürgen . Arčon . Denis . Jansen . Martin . Felser . Claudia . Verwey-type charge ordering transition in an open-shell p -electron compound . Science Advances . American Association for the Advancement of Science (AAAS) . 4 . 1 . 2018-01-17 . eaap7581 . 2375-2548 . 10.1126/sciadv.aap7581 . 29372183 . 5775027 . 2018SciA....4.7581A . free.
  8. Colman . Ross H. . Okur . H. Esma . Kockelmann . Winfried . Brown . Craig M. . Sans . Annette . Felser . Claudia . Jansen . Martin . Prassides . Kosmas . Elusive Valence Transition in Mixed-Valence Sesquioxide Cs4O6 . Inorganic Chemistry . American Chemical Society (ACS) . 58 . 21 . 2019-10-21 . 0020-1669 . 10.1021/acs.inorgchem.9b02122 . 14532–14541. 31633914 . 7880551.
  9. Attema . J J . Wijs . G A de . Groot . R A de . Spintronic materials based on main-group elements . Journal of Physics: Condensed Matter . IOP Publishing . 19 . 16 . 2007-04-05 . 0953-8984 . 10.1088/0953-8984/19/16/165203 . 165203. 2007JPCM...19p5203A . 98543752 .
  10. Okur . H. Esma . Colman . Ross H. . Ohishi . Yasuo . Sans . Annette . Felser . Claudia . Jansen . Martin . Prassides . Kosmas . Pressure-Induced Charge Disorder–Order Transition in the Cs4O6 Sesquioxide . Inorganic Chemistry . American Chemical Society (ACS) . 59 . 2 . 2020-01-06 . 0020-1669 . 10.1021/acs.inorgchem.9b02974 . 1256–1264. 31904961 . 210041198.
  11. Arčon . D. . Anderle . K. . Klanjšek . M. . Sans . A. . Mühle . C. . Adler . P. . Schnelle . W. . Jansen . M. . Felser . C. . Influence of O2 molecular orientation on p-orbital ordering and exchange pathways in Cs4O6 . Physical Review B . American Physical Society (APS) . 88 . 22 . 2013-12-10 . 1098-0121 . 10.1103/physrevb.88.224409 . 224409. 2013PhRvB..88v4409A.

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