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.

Theoretical studies of the air-water interface of a water droplet show a wide distribution of strong electric fields at the surface that can make or break chemical bonds to accelerate chemical reactions over the bulk water phase.

Details

Title
Can electric fields drive chemistry for an aqueous microdroplet?
Author
Hao Hongxia 1   VIAFID ORCID Logo  ; Leven Itai 1 ; Head-Gordon, Teresa 2   VIAFID ORCID Logo 

1  University of California, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA (GRID:grid.47840.3f) (ISNI:0000 0001 2181 7878); University of California, Pitzer Center for Theoretical Chemistry, Berkeley, USA (GRID:grid.47840.3f) (ISNI:0000 0001 2181 7878); University of California, Departments of Chemistry, Berkeley, USA (GRID:grid.47840.3f) (ISNI:0000 0001 2181 7878) 
2  University of California, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA (GRID:grid.47840.3f) (ISNI:0000 0001 2181 7878); University of California, Pitzer Center for Theoretical Chemistry, Berkeley, USA (GRID:grid.47840.3f) (ISNI:0000 0001 2181 7878); University of California, Departments of Chemistry, Berkeley, USA (GRID:grid.47840.3f) (ISNI:0000 0001 2181 7878); University of California, Departments of Bioengineering, Berkeley, USA (GRID:grid.47840.3f) (ISNI:0000 0001 2181 7878); University of California, Departments of Chemical and Biomolecular Engineering, Berkeley, USA (GRID:grid.47840.3f) (ISNI:0000 0001 2181 7878) 
Publication year
2022
Publication date
2022
Publisher
Nature Publishing Group
e-ISSN
20411723
Source type
Scholarly Journal
Language of publication
English
DOI
https://doi.org/10.1038/s41467-021-27941-x
ProQuest document ID
2619056269
Copyright
© The Author(s) 2022. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.