Influence of Water on the Oxidation of Dimethyl Sulfide by the ·OH Radical - Sorbonne Université Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry B Année : 2017

Influence of Water on the Oxidation of Dimethyl Sulfide by the ·OH Radical

Résumé

Oxidative stress of sulfur-containing biological molecules in aqueous environments may lead to the formation of adduct intermediates that are too short-lived to be experimentally detectable. In this study we have modeled the simplest of such oxidative reactions: the attack of dimethyl sulfide (DMS) by a hydroxyl radical (·OH) to form a radical adduct, whose subsequent heterolytic dissociation leads to a radical cation (DMS+) that is important for further reactions. We have modeled the aqueous environment with a limited number of discrete water molecules, selected after an original multistep procedure, and further embedded in a polarizable continuum model, to observe the impact of the water configuration on the heterolytic dissociation of the radical adduct. Molecular dynamics and quantum chemical methods (DFT, MP2, and CCSD) were used to elucidate the lowest energy structures resulting from the ·OH attack on DMS. Subsequent high level ab initio valence bond (BOVB) calculations revealed the possibility for the occurrence of subsequent heterolytic dissociation.
Fichier principal
Vignette du fichier
Domin_2017_On_the_Influence_of.pdf (762.51 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-01634956 , version 1 (14-11-2017)

Identifiants

Citer

Dominik Domin, Benoît Braïda, Jacqueline Bergès. Influence of Water on the Oxidation of Dimethyl Sulfide by the ·OH Radical. Journal of Physical Chemistry B, 2017, 121 (40), pp.9321-9330. ⟨10.1021/acs.jpcb.7b05796⟩. ⟨hal-01634956⟩
268 Consultations
178 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More