Please use this identifier to cite or link to this item: http://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: http://hdl.handle.net/10316/8276
DOI: 10.1002/chem.200500727
Rights: openAccess
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais

Files in This Item:
File Description SizeFormat
obra.pdf333.38 kBAdobe PDFView/Open
Show full item record

Page view(s)

61
checked on Sep 17, 2019

Download(s)

34
checked on Sep 17, 2019

Google ScholarTM

Check

Altmetric

Dimensions


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.