Electric fields drive bond homolysis

17 October 2022, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Electric fields have been used to control and direct chemical reactions in biochemistry and enzymatic catalysis, yet directly applying external electric fields to activate reactions in bulk solution and to characterize them ex situ remains a challenge. Here we utilize the scanning tunneling microscope-based break-junction technique to investigate the electric field driven homolytic cleavage of the radical initiator 4-(methylthio)benzoic peroxyanhydride at ambient temperatures in bulk solution, without the use of co-initiators or photochemical activators. Through ex-situ quantification by high performance liquid chromatography and UV-vis analysis as a function of time, we find that the electric field catalyzes the reaction. Importantly, we demonstrate that the reaction rate in a field increases linearly with solvent dielectric constant. Using density functional theory calculations, we show that the applied electric field decreases the dissociation energy of the O-O bond and stabilizes the product relative to the reactant due to their different dipole moments.


Electric Field Catalysis
Bond Homolysis
Green Chemistry
Single-Molecule Conductance

Supplementary materials

Supplementary Information for: Electric fields drive bond homolysis
Supplementary Notes Supplementary Figures 1-11


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