Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/5175
Title: Intersecting-state model calculations on fast and ultrafast excited-state proton transfers in naphthols and substituted naphthols
Authors: Barroso, Mónica 
Arnaut, Luís G. 
Formosinho, Sebastião J. 
Keywords: Excited-state proton transfer; Proton-transfer rates; Naphthol; Intersecting-state model; Kinetic isotope effects
Issue Date: 2002
Citation: Journal of Photochemistry and Photobiology A: Chemistry. 154:1 (2002) 13-21
Abstract: The intersecting-state model (ISM) is applied to the calculation of absolute rate constants for proton-transfer reactions of naphthols and substituted naphthols in the first singlet state and for ground states. ISM incorporates quantum-mechanical tunnelling, zero-point energy corrections and an electrophilicity parameter to account for the lowering of the binding energy of transition states. Good agreement with experimental rates is observed over 12 orders of magnitude. The lower reactivity of the photoacids in alcohols when compared to the behaviour in water can be accounted for the differences in the potential energy curves of the OH bonds. Patterns of reactivity with respect to free-energy relations and kinetic isotope effects are also discussed.
URI: http://hdl.handle.net/10316/5175
Rights: openAccess
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais

Files in This Item:
File Description SizeFormat
file7fa4b6d8a3a64390a81ab78d871060e6.pdf30.95 kBAdobe PDFView/Open
Show full item record

Page view(s)

134
checked on Apr 9, 2020

Download(s) 50

222
checked on Apr 9, 2020

Google ScholarTM

Check


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