Please use this identifier to cite or link to this item:
https://hdl.handle.net/10316/5091
Title: | Tunnelling in low-temperature hydrogen-atom and proton transfers | Authors: | Arnaut, Luís G. Formosinho, Sebastião J. Barroso, Mónica |
Keywords: | Tunnelling; Proton transfer; Hydrogen atom transfer; Tautomerism | Issue Date: | 2006 | Citation: | Journal of Molecular Structure. 786:2-3 (2006) 207-214 | Abstract: | The reaction path of the interacting-state model with the Lippincott-Schroeder potential for hydrogen bonds, is used in transition-state theory calculations with the semiclassical correction for tunnelling (LS-ISM/scTST) to estimate proton and hydrogen-atom transfer rates at low temperatures. Down to 100 K, the semiclassical correction leads to semi-empirical rates and isotope effects that are in good agreement with the thermal tautomerism of porphine, and the excited-state tautomerisms of salicylideneanilines and 2-(2'-hydroxyphenyl)benzoxazole. For lower temperatures, the tunnelling corrections become extremely high and unreliable. It is shown that the permeability of an Eckart barrier fitted to the curvature of the LS-ISM reaction path leads to good estimates of these reaction rates down to 2 K. | URI: | https://hdl.handle.net/10316/5091 | DOI: | 10.1016/j.molstruc.2005.10.002 | Rights: | openAccess |
Appears in Collections: | FCTUC Química - Artigos em Revistas Internacionais |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
file97253c3558a54b53a7d960753209b56b.pdf | 175.42 kB | Adobe PDF | View/Open |
SCOPUSTM
Citations
20
checked on Sep 30, 2024
WEB OF SCIENCETM
Citations
19
checked on Sep 2, 2024
Page view(s)
316
checked on Sep 24, 2024
Download(s) 50
446
checked on Sep 24, 2024
Google ScholarTM
Check
Altmetric
Altmetric
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.