My research interest is in the use of quantum mechanical, molecular orbital methods to investigate the structure, properties, and reaction rates of a variety of species. The species studied are characterized by being small molecules of interest because of their spectroscopic properties, their unusual bonding, or their reactivity. Recent studies have focused on species thought to play an important role in atmospheric chemistry and particularly the reaction of radicals with CFC's, ozone, and nitrogen oxides. In particular we continue to examine the very difficult problem of the reaction between ozone and chlorine. This is complicated by the multiconfigurational nature of both ozone and the chlorine atom and the fact that the transition state for the reaction involves a very long Cl - O3 interaction which is primarily dispersion based. The barrier for the reaction is very low - approximately 0.5 kcal/mol. These factors test the current limits of quantitative molecular orbital calculations.
The nature of bonding in species such as ONF3, OCF3-, and FNO2 is being investigated. These compounds show a significant discrepancy between their structures (especially bond lengths) relative to what would be predicted based on their Lewis structure. The importance of ionic character, ionic resonance forms and hypervalency are considered.
The structure and thermodynamic properties of H2O3 and a series of related isoelectronic species are being investigated to determine their stability or lack of stability and the reasons for that.