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Tetraoxygen
The tetraoxygen molecule (O4) was first predicted in 1924 by Gilbert N. Lewis, who proposed it as an explanation for the failure of liquid oxygen to obey Curie's law.[1] Today it seems Lewis was off, but not by far: computer simulations indicate that although there are no stable O4 molecules in liquid oxygen, O2 molecules do tend to associate in pairs with antiparallel spins, forming transient O4 units.[2] True O4 does exist, however, as a stable red solid at pressures above 10 GPa.[3] This phase is known as ε oxygen or red oxygen. Tetraoxygen has also been detected as a short-lived chemical species in mass spectrometry experiments.[4] Red oxygenAs the pressure of oxygen at room temperature is increased through 10 GPa, it undergoes a dramatic phase transition to a different allotrope. Its volume decreases significantly,[5] and it changes color from blue to deep red.[6] Based on its infrared absorption spectrum, this phase is believed to consist of O4 molecules in a crystal lattice.[3] Liquid oxygen is already used as a rocket fuel, and it has been speculated that red oxygen could make an even better fuel, because of its higher energy density.[7] At 96 GPa, oxygen undergoes another phase transition and becomes metallic.[5] Free moleculeTheoretical calculations have predicted the existence of metastable O4 molecules with two different shapes: a "puckered" square like cyclobutane,[8] and a "pinwheel" with three oxygen atoms surrounding a central one.[9] In 2001, a team at the University of Rome La Sapienza conducted a neutralization-reionization mass spectrometry experiment to investigate the structure of free O4 molecules.[4] Their results did not agree with either of the two proposed molecular structures, but they did agree with a complex between two O2 molecules, one in the ground state and the other in a specific excited state. See also
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This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Tetraoxygen". A list of authors is available in Wikipedia. |