Computational forays into the electronic structure of radicals

Quantum chemical studies are presented on several gas-phase radicals. The first project details computations of the properties of the methylsulfinyl radical, which is central to remote marine atmospheric sulfur chemistry. The second explores the mechanism of the reaction between ozone and the methylsulfinyl radical, showing that a previous theoretical study vastly overestimated the reaction barrier, likely as a result of improper method choice. The focus then shifts to radicals found in the combustion of butanol; computations of infrared frequencies resulted in suggested reassignments of several experimental modes. Finally, the interactions of uracil with neutral alkali metal atoms appear to involve substantial transfer of the unpaired electron to the nucleobase, despite the low electron affinity of the latter.