Electric fields drive bond homolysis.
Boyuan ZhangCedric SchaackClaudia R PrindleEthan A VoMiriam AzizMichael L SteigerwaldTimothy C BerkelbachColin P NuckollsLatha VenkataramanPublished in: Chemical science (2023)
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 time-dependent ex situ quantification by high performance liquid chromatography using a UV-vis detector, we find that the electric field catalyzes the reaction. Importantly, we demonstrate that the reaction rate in a field increases linearly with the 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.
Keyphrases
- density functional theory
- high performance liquid chromatography
- molecular dynamics
- electron transfer
- tandem mass spectrometry
- mass spectrometry
- simultaneous determination
- solid phase extraction
- air pollution
- high resolution
- particulate matter
- hydrogen peroxide
- ionic liquid
- transition metal
- transcription factor
- nitric oxide