Theory of Chemical Reactions in Solution

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In this project in the Physical Chemistry Program, Hynes will formulate theoretical descriptions of and perform numerical calculations on several important types of chemical reactions in solution. The particular focus is on determining, understanding and predicting how the surrounding liquid solvent can alter the rates of these reactions. Computer simulations of electron transfer reactions, of the type important in electrochemistry, will be carried out to determine the role played by the motion of the solvent molecules in determining the reaction rates. Related simulations of fluorescent radiation emitted after laser excitation will further elucidate this role. Theoretical and numerical studies will be undertaken for proton transfer reactions of the type important in acid-base chemistry and catalysis. An important feature here is determination of the role played by quantum mechanical tunneling in the reactions and how this could be affected by the solvent. Theoretical studies will also be performed to understand and predict the fundamental mechanism of ionic dissociation reactions in solution and how the solvent can drastically alter the reaction behavior compared to the gas phase. A final set of theoretical studies will determine how a solvent might sufficiently alter the flow of energy inside a highly vibrationally excited and reactive molecule to enhance the rate of the reaction.