Abstract
Reaction rates of common organic reactions have been reported to increase by one to six orders of magnitude in aqueous microdroplets compared to bulk solution, but the reasons for the rate acceleration are poorly understood. Using a coarse-grained electron model that describes structural organization and electron densities for water droplets without the expense of ab initio methods, we investigate the electric field distributions at the air-water interface to understand the origin of surface reactivity. We find that electric field alignments along free O–H bonds at the surface are ~16 MV/cm larger on average than that found for O–H bonds in the interior of the water droplet. Furthermore, electric field distributions can be an order of magnitude larger than the average due to non-linear coupling of intramolecular solvent polarization with intermolecular solvent modes which may contribute to even greater surface reactivity for weakening or breaking chemical bonds at the droplet surface.
Highlights
Reaction rates of common organic reactions have been reported to increase by one to six orders of magnitude in aqueous microdroplets compared to bulk solution, but the reasons for the rate acceleration are poorly understood
Recent exciting work has shown that seemingly simple water droplets give rise to unexpected rate accelerations for organic reactions by factors of one to six orders of magnitude compared to the bulk liquid[1,2]
In particular we find field strengths that increase to an average of ~16 MV/cm, enough to activate strong bonds or break weak chemical bonds, with a wide distribution of field strengths that can reach an order of magnitude larger to drive faster chemical reactions
Summary
Reaction rates of common organic reactions have been reported to increase by one to six orders of magnitude in aqueous microdroplets compared to bulk solution, but the reasons for the rate acceleration are poorly understood. Using a coarse-grained electron model that describes structural organization and electron densities for water droplets without the expense of ab initio methods, we investigate the electric field distributions at the air-water interface to understand the origin of surface reactivity. Electric field distributions can be an order of magnitude larger than the average due to non-linear coupling of intramolecular solvent polarization with intermolecular solvent modes which may contribute to even greater surface reactivity for weakening or breaking chemical bonds at the droplet surface. In particular we find field strengths that increase to an average of ~16 MV/cm, enough to activate strong bonds or break weak chemical bonds, with a wide distribution of field strengths that can reach an order of magnitude larger to drive faster chemical reactions
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