Microscopic Analysis of Dynamics-Controlled Organic Reactions

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A combined computational-experimental study was carried out to examine dynamics effects in organic reactions. A fragment molecular orbital-molecular dynamics method (FMO-MD) was developed and used to analyze microscopic reaction mechanisms, in particular the active role of solvent molecules, in amination and hydration reactions of aldehyde in water. Ab initio MD simulations were performed for selected organic reactions, such as molecular rearrangement, elimination, addition, and substitution reactions. These computational studies revealed that the reaction products were determined through path bifurcation after the rate-determining transition state. Experimental studies using kinetic measurements and product analyses gave the results that supported the conclusion on the basis of the MD simulations. These results demonstrated that reaction dynamics play important role in determining the reaction mechanism and may require modification of the traditional transition state theory.