Charge transfer reactions such as electron and ion transfer as well as reactions with a significant difference in charge distribution between the reactants and the transition state (such as S<sub>N</sub>2 and ionization reactions) are very sensitive to the solvent polarity. The dynamics and thermodynamics of these reactions are strongly influenced by the heterogeneous character of the liquid/liquid and liquid/vapor interfaces where the polarity of the media changes rapidly over a sub-nanometer length scale. Surface-active molecules adsorbed at the interface (such as phase-transfer catalysts) can provide a local reaction environment whose polarity is further distinguished from that of the neat interface. We examine using molecular dynamics computer simulations how these surface-active molecules affect reactivity and how their effect is influenced by the local structure and dynamics of the interface. As examples, we consider the effect on S<sub>N</sub>2 reactions of cyclodextrin at the water/oil interface and the effect on charge recombination reactions of alkyl ammonium at the glycerol surface.

Influence of surface-active molecules on reactions at liquid interfaces: Molecular dynamics studies

255th National Meeting (2018)

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