Electric Field Effects on Excited State and Electron Transfer Dynamics

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This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research by Dr. Steven G. Boxer of the Chemistry Department, Stanford University, for investigation of the photophysics and reaction dynamics of coordination complexes in applied electric fields. A Stark spectrometer based on a step-scan FTIR will be developed for use in obtaining high signal-to-noise virbrational Stark effect spectra in the mid-IR region and electronic Stark spectra for the broad transitions characteristic of coordination compounds. Some of the specific problems to be investigated by Stark spectroscopy include: electronic coupling in class II mixed valence complexes and metal-bridged prophyrin dimers; bond anharmonicity in carbonyl and C-F stretches; degree of delocalization in push-pull polyenes (used in non-linear optical devices) imposed by large internal electric fields that result from the attachment of strong electron donors and acceptors; effect of applied electric fields on excited state proton transfer reactions in 3-hydroxyflavone. Interactions between molecular fragments separated by relatively long and chemically interesting spacers will be investigated using Stark effect spectroscopy. Electronic or vibrational transitions are affected by applied electric fields and measurement of this effect provides quantitative information on the magnitude and direction of charge displacement. Electric fields can also be used to manipulate the rates of electron and proton transfer reactions. The results are not only of fundamental interest but also potentially applicable to the development of non-linear optical materials for use in the electronics industry.