Radical -molecule *complexes in Earth's atmosphere
Abstract
The purpose of this present research is to explore the role radical-molecule complexes may play in the chemistry of Earth's atmosphere. Complexes of all kinds are known to exist in Earth's atmosphere, but so far have been elusive to researchers for many reasons. Among them are difficulty in distinguishing the complex from its parent monomers, short lifetimes due to the fact that they are weakly bound, and uncertainty in the amount of complex present, due to lack of knowing the energetics of complex formation. In the laboratory, it has been shown that complexes play an important role in atmospheric chemistry by having differing reactivities than those of their parent monomers, by have differing photochemistry than the monomers, and by being the precursors to aerosol formation. There are a handful of studies that examine examples of each of these cases. These examples end up being critical for the understanding of essential atmospheric processes, however. Radicals play an important role in the chemistry of the Earth, in that they initiate most of the chemical processes that take place. In this study, we examine the possibilities of radicals forming complexes with more abundant molecules in the atmosphere. Both theoretical calculations and experimental methods are employed to do this. Numerous new radical-molecule complexes are identified as a result of this. Special attention is given to spectroscopic properties of these complexes that differ from those of the parent monomers, in order to provide a means of identification of these complexes. The energetics of these complexes are explored. Equilibrium concentrations and lifetimes of the complexes are estimated. These data are used to predict the atmospheric implications of the existence of these complexes. Recommendations for further research are made in the final section of this thesis.
Degree
Ph.D.
Advisors
Francisco, Purdue University.
Subject Area
Analytical chemistry|Chemistry
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