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Photoelectron Spectroscopy of Solvated Electrons in Liquid Microjets


This dissertation presents studies of the binding energies of solvated electrons in a variety of solutions. Solvated electrons play an important role in radiation chemistry and biology, and have been the subject of many studies since their discovery over a century ago. Information on their binding energies, however, has been limited to the results of theoretical calculations or inference from work with small solvent clusters. To directly measure the solvated electron vertical binding energies (VBEs) in bulk solution, a new apparatus was constructed coupling a liquid microjet source to a photoelectron spectrometer. Using two photons from individual pulses of a nanosecond laser, solvated electrons were generated and detached to vacuum. Their kinetic energies were then measured with a field-free time-of-flight spectrometer.

Studies are presented here that utilize this apparatus to measure the VBEs of solvated electrons in water, methanol, ethanol, and acetonitrile. Preliminary efforts to study solvated electrons in tetrahydrofuran are also described. The findings of these studies are compared to past work on small solvent clusters, doped with either an excess electron or an alkali metal atom.

A second generation liquid microjet apparatus is also described. Using a magnetic bottle time-of-flight spectrometer, the collection efficiency of the next generation apparatus will be significantly higher than the original apparatus.

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