Microhydration and the enhanced acidity of free radicals
Abstract
Recent theoretical research employing a continuum solvent model predicted that radical centers would enhance the acidity (RED-shift) of certain proton-donor molecules. Microhydration studies employing a DFT method are reported here with the aim of establishing the effect of the solvent micro-structure on the acidity of radicals with and without RED-shifts. Microhydration cluster structures were obtained for carboxyl, carboxy-ethynyl, carboxy-methyl, and hydroperoxyl radicals. The numbers of water molecules needed to induce spontaneous ionization were determined. The hydration clusters formed primarily round the CO2 units of the carboxylate-containing radicals. Only 4 or 5 water molecules were needed to induce ionization of carboxyl and carboxy-ethynyl radicals, thus corroborating their large RED-shifts.
Citation
Walton , J C 2018 , ' Microhydration and the enhanced acidity of free radicals ' , Molecules , vol. 23 , no. 2 , 423 . https://doi.org/10.3390/molecules23020423
Publication
Molecules
Status
Peer reviewed
ISSN
1420-3049Type
Journal article
Rights
Copyright 2018 the author. This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).
Description
The author thanks EaStCHEM for financial support.Collections
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.