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Protonation of Water Clusters Induced by Hydroperoxyl Radical Surface Adsorption
Author(s) -
TorrentSucarrat Miquel,
RuizLopez Manuel F.,
MartinsCosta Marilia,
Francisco Joseph S.,
Anglada Josep M.
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002706
Subject(s) - hydroperoxyl , chemistry , dissociation (chemistry) , protonation , radical , water cluster , cluster (spacecraft) , adsorption , hydronium , molecule , hydroxide , photochemistry , hydrogen bond , autoionization , self ionization of water , inorganic chemistry , ion , organic chemistry , photoionization , ionization , computer science , programming language
We have investigated the HO 2 adsorption and acid dissociation process on the surface of (H 2 O) 20 and (H 2 O) 21 clusters by using quantum‐chemistry calculations. Our results show that the radical forms a stable hydrogen‐bond complex on the cluster. The HO 2 acid dissociation is more favorable in the case of the (H 2 O) 21 cluster, for which the inner water molecule plays a crucial role. In fact, acid dissociation of HO 2 is found to occur in two steps. The first step involves H 2 O autoionization in the cluster, and the second one involves the proton transfer from the HO 2 radical to the hydroxide anion. The presence of the HO 2 radicals on the surface of the cluster facilitates water autoionization in the cluster.

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