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Spectroscopic determination of hydrogen bonding in anionic clusters

Posted on:2006-09-13Degree:Ph.DType:Dissertation
University:Yale UniversityCandidate:Price, Erica AnneFull Text:PDF
GTID:1451390008474902Subject:Chemistry
Abstract/Summary:
Scientific research in the area of gas-phase clusters can uncover elementary chemical properties and processes because of the ability to isolate the mass-resolved species of interest. These discoveries are crucial to experiments in the condensed phase where a fundamental understanding is necessary to disentangle the ensemble of results. Water is the most important solvent in life systems and yet the nature of the hydrogen bonding that guides solvation is not fully understood. This dissertation explores the regime where water molecules are limited to weaker hydrogen bonds delocalized over the two protons. This symmetrical binding of water is seen in SO2-·H2O and Cl2-·(H2O) 1--2 and exhibits very unique features in the vibrational spectrum. Also, this work presents the water cluster model for the "hydrated electron" solvation dynamics greatly debated in recent literature. Femtosecond photoelectron spectroscopy of (H2O)-20--100 can discriminate whether a detached electron originated in the excited state or the ground state, allowing lifetime measurement of the transient pre-solvated state. Most past, present, and future experimental research would be remain greatly unidentified without the associated understanding brought about through theoretical work. A chapter is devoted to methods developed to elucidate the complicated vibrational picture of a system, OH-·CH 3, where two low frequency modes involving proton motion are coupled.
Keywords/Search Tags:Hydrogen
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