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Dication

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A dication is any cation, of general formula X2+, formed by the removal of two electrons from a neutral species.

Diatomic dications corresponding to stable neutral species (e.g. H2+
2
formed by removal of two electrons from H2) often decay quickly into two singly charged particles (H+), due to the loss of electrons in bonding molecular orbitals. Energy levels of diatomic dications can be studied with good resolution by measuring the yield of pairs of zero-kinetic-energy electrons from double photoionization of a molecule as a function of the photoionizing wavelength (threshold photoelectrons coincidence spectroscopy – TPEsCO). The He2+
2
dication is kinetically stable.

An example of a stable diatomic dication which is not formed by oxidation of a neutral diatomic molecule is the dimercury dication Hg2+
2
. An example of a polyatomic dication is S2+
8
, formed by oxidation of S8 and unstable with respect to further oxidation over time to form SO2.

Many organic dications can be detected in mass spectrometry for example CH2+
4
(a CH2+
2
·H
2
complex) and the acetylene dication C
2
H2+
2
.[1] The adamantyl dication has been synthesized.[2] The adamantane dication

Divalent metals

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Common element dications
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson

Some metals are commonly found in the form of dications when in the form of salts, or dissolved in water. Examples include the alkaline earth metals (Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Ra2+); later 3d transition metals (V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+); group 12 elements (Zn2+, Cd2+, Hg2+); and the heavy members of the carbon group (Sn2+, Pb2+).

Presence in space

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Multiply-charged atoms are quite common in the Solar system in the so-called Solar wind. Among these, the most abundant dication is He2+. However, molecular dications, in particular CO22+, have never been observed so far though predicted to be present for instance at Mars.[3] Indeed, this ion by means of its symmetry and strong double bounds is more stable (longer lifetime) than other dications. In 2020, the molecular dication CO22+ has been confirmed to be present in the atmosphere of Mars[4] and around Comet 67P.[5]

References

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  1. ^ Lammertsma, K.; von Ragué Schleyer, P.; Schwarz, H. (1989). "Organic Dications: Gas Phase Experiments and Theory in Concert". Angew. Chem. Int. Ed. Engl. 28 (10): 1321–1341. doi:10.1002/anie.198913211.
  2. ^ Bremer, Matthias; von Ragué Schleyer, Paul; Schötz, Karl; Kausch, Michael; Schindler, Michael (August 1987). "Four-Center Two-Electron Bonding in a Tetrahedral Topology. Experimental Realization of Three-Dimensional Homoaromaticity in the 1,3-Dehydro-5,7-adamantanediyl Dication". Angewandte Chemie International Edition in English. 26 (8): 761–763. doi:10.1002/anie.198707611. ISSN 0570-0833.
  3. ^ Witasse, O.; Dutuit, O.; Lilensten, J.; Thissen, R.; Zabka, J.; Alcaraz, C.; Blelly, P.-L.; Bougher, S. W.; Engel, S.; Andersen, L.H.; Seiersen, K. (2020). "Prediction of a CO22+ layer in the atmosphere of Mars". Geophysical Research Letters. 29 (8): 104-1–104-4. doi:10.1029/2002GL014781. S2CID 129035959.
  4. ^ Gu, H.; Cui, J.; Diu, D.; Dai, L.; Huang, J.; Wu, X.; Hao, Y.; Wei, Y. (2020). "Observation of CO22+ dication in the dayside Martian upper atmosphere". Earth and Planetary Physics. 4 (4): 396–402. doi:10.26464/epp2020036. S2CID 219929017.
  5. ^ Beth, A.; Altwegg, K.; Balsiger, H.; Berthelier, J.-J.; Combi, M. R.; De Keyser, J.; Fiethe, B.; Fuselier, S.A.; Galand, M.; Gombosi, T.I.; Rubin, M.; Sémon, T. (2020). "ROSINA ion zoo at Comet 67P". Astronomy and Astrophysics. 642 (October 2020): A27. arXiv:2008.08430. doi:10.1051/0004-6361/201936775. S2CID 221172890.