Date of Award

Fall 2013

Project Type


Program or Major


Degree Name

Master of Science

First Advisor

Howard R Mayne


Experimental determination of rate constants for gas phase radical reactions is challenging. When rate constants necessary for modeling complex processes in atmospheric and combustion science are unknown, theoretical predictions are useful. We used Variational Transition State Theory with Multidimensional Tunneling (VTST/MT) with Density Functional Theory (DFT) to calculate the rate constant and isotope effects for reaction between the peroxymethyl radical and the hydrogen atom.

Polychlorinated dibenzofurans (PCDFs) are a group of extremely toxic compounds formed during waste incineration. Currently, their chemical degradation in the atmosphere is poorly understood. While some experimental and theoretical results regarding the reaction of PCDFs with the hydroxyl radical are available, to our knowledge, no group has studied their reaction with another important atmospheric oxidant, the chlorine atom (Cl). As a first step in this direction, we have characterized the potential energy surface for reaction between the parent compound of PCDFs, dibenzofuran, and Cl using DFT.