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The first decrease in rate is typical of the \u201cinverted region\u201d of electron\u2010transfer reactions. The change to an increase in the rate for ultra\u2010exothermic electron transfer indicates a new free\u2010energy relationship. We show that the resulting \u201cdouble\u2010inverted region\u201d is not due to a change in mechanism. It is an intrinsic property of electron\u2010transfer reactions, and it is due to the increase of the reorganisation energy with the reaction exothermicity.<\/jats:p>","DOI":"10.1002\/chem.200500727","type":"journal-article","created":{"date-parts":[[2006,3,20]],"date-time":"2006-03-20T06:18:42Z","timestamp":1142835522000},"page":"5014-5023","source":"Crossref","is-referenced-by-count":20,"title":["Electron Transfer in Supercritical Carbon Dioxide: Ultraexothermic Charge Recombination at the End of the \u201cInverted Region\u201d"],"prefix":"10.1002","volume":"12","author":[{"given":"Carlos","family":"Serpa","sequence":"first","affiliation":[]},{"given":"Paulo J. S.","family":"Gomes","sequence":"additional","affiliation":[]},{"given":"Luis G.","family":"Arnaut","sequence":"additional","affiliation":[]},{"given":"Sebasti\u00e3o J.","family":"Formosinho","sequence":"additional","affiliation":[]},{"given":"Jo\u00e3o","family":"Pina","sequence":"additional","affiliation":[]},{"given":"J. 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