Sustaining local electric fields in confined microscopic environments as polarizing agents for catalyzing reactions is important. It is argued that many enzymes operate based on this principle and lessons learned from them can be extended to other catalytic systems. We use Stark shift spectroscopy to measure electric fields at electrochemical interfaces for understanding solvation, interfacial polarization, molecular structure, steric hindrance, and frustrated bond formation. We will present experimental results on fields at the junction of electrolytes and biased metal electrodes. Both simple dilute electrolytes that are mostly described by the continuum Gouy-Chapman model and its variants, and ionic liquids which deviate from such a description will be discussed. Results on the connection between a polarizing electric field at an electrochemical interface and the polarizing effect of organic substituents in homogenous catalysis will also be presented. A major challenge is engineering and designing local environments that can sustain such fields. With inspiration from the relatively new field of Frustrated Lewis Pairs (FLPs), we report our results on Lewis bonds near a surface. We comment on the electric field perspective of the mechanism of FLP catalysis and propose approaches on how to use frustrated Lewis pairs as polarizing environments near an electrode for driving reactions. We also present computational results that establish a connection between the strength of a chemical bond and the electric field needed to break it. In particular, we show that electric fields are capable of breaking dative bonds even when there is no explicit redox reaction involved. This helps solidify the fundamental connections between fields and chemical bonds.

Electric fields, catalysis, and electrochemistry: A stark shift spectroscopy perspective

2019 Spring National Meeting

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