Dynamics of Gas Phase Organic Reactions

Columbia University, New York NY

Investigators

Abstract

With this new award, the Organic and Macromolecular Chemistry Program supports the work of Professor Charles Doubleday of the Chemistry Department at Columbia University. This research will involve investigations of the dynamics of gas phase organic reactions. The project builds on previous work of the PI to expand the scope of reactions in which nonstatistical dynamics is studied. In addition to unimolecular isomerizations, which have yielded much insight on the factors that govern a nonstatistical product ratio and the type of reaction in which nonstatistical dynamics can be expected, this project will study bimolecular reactions of oxygen with neutral radicals and also an ion-neutral reaction. These strongly exothermic reactions have the energetic capability to give nonstatistical product ratios, and preliminary results are consistent with this. The focus of this project will be on developing methods for the accurate calculation of the directly formed product ratio, and to develop simple models for a clear qualitative understanding of the results. Systems to be investigated include the combustion related reaction of oxygen with vinyl and phenyl radicals, the gas phase ion molecule reaction of hydroxide with methyl formate, and a series of unimolecular isomerizations. This research will lead to improvement in kinetic models of reactions that are important in combustion, air quality studies, and human health generally. These studies will result in the training of junior research collaborators and the consequent strengthening of scientific infrastructure. Dissemination of computer code, developed in these investigations, will allow the scientific community to investigate other reactions using these sophisticated techniques.