Please use this identifier to cite or link to this item:
https://hdl.handle.net/10316/8276
Title: | Electron Transfer in Supercritical Carbon Dioxide: Ultraexothermic Charge Recombination at the End of the ldquoInverted Regionrdquo | Authors: | Serpa, Carlos Gomes, Paulo J. S. Arnaut, Luis G. Formosinho, Sebastião J. Pina, João Melo, J. Seixas de |
Issue Date: | 2006 | Citation: | Chemistry - A European Journal. 12:19 (2006) 5014-5023 | Abstract: | Charge-recombination rates in contact radical-ion pairs, formed between aromatic hydrocarbons and nitriles in supercritical CO2 and heptane, decrease with the exothermicity of the reactions until they reach -70 kcal mol-1, but from there on an increase is observed. The first decrease in rate is typical of the ldquoinverted regionrdquo of electron-transfer reactions. The change to an increase in the rate for ultra-exothermic electron transfer indicates a new free-energy relationship. We show that the resulting ldquodouble-inverted regionrdquo is not due to a change in mechanism. It is an intrinsic property of electron-transfer reactions, and it is due to the increase of the reorganisation energy with the reaction exothermicity. | URI: | https://hdl.handle.net/10316/8276 | DOI: | 10.1002/chem.200500727 | Rights: | openAccess |
Appears in Collections: | FCTUC Química - Artigos em Revistas Internacionais |
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