Understanding local electric fields in confined environments and interfaces is ubiquitously important in a wide spectrum of physical and chemical phenomena ranging from device physics to electrochemistry and catalysis. Modeling and measurements of such fields is often difficult due to the complexity and experimental inaccessibility of such environments. We will present various applications of vibrational Stark shift spectroscopy using benzonitrile as a probe molecule for measurement of such fields at electrochemical interfaces. Experimental results on electric fields arising from interactions of a dielectric and a metal at equilibrium, along with an interfacial solvation model analogous to Onsager’s theory, will be discussed. Then results and models for electric fields at biased electrode-electrolyte junctions along with the limits of the applicability of the Gouy-Chapman theory will be presented. Stark shift spectroscopy is used to study the complex environment of ionic liquids at a metal interface, and information about the local electric fields and ionic arrangements is revealed. With a vision of engineering highly polarizing environments at a surface, preliminary results on how to perceive homogenous frustrated Lewis acid-base catalysis as a field effect and create its analogues at electrochemical interfaces will be presented.

Stark shift spectroscopy for measurement of electric fields at interfaces

2019 Spring National Meeting

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.