Fundamental Studies of Electron-Molecule Reactions
The reaction between an electron and a molecule in the gas phase is one of the most fundamental yet the chemistry that takes place can be extremely complex. Our goal is to develop a thorough understanding of the kinetics and mechanisms of electron-molecule reactions so that their role in the chemistry of natural and man-made environments can be determined and even exploited. We approach this work both experimentally and computationally. Experiments study the kinetics and products of individual reactions using the Flowing Afterglow Langmuir Probe technique coupled with mass spectral analysis. Temperature and electron kinetic energy dependences of the reaction kinetics and product branching fractions are determined. Molecular properties are studied computationally using ab initio and semi-empirical methods while complex kinetics are revealed with numerical kinetic models. This multi-faceted approach allows us to to reveal the essential features of these reactions and their mechanisms.
Representative Publications:"G3 and density functional theory investigations of the structures and energies of SFnCl (n=0-5) and their anions," J.M. Van Doren, T.M. Miller, and A.A. Viggiano, J. Chem. Phys., accepted October 2007.
"Observation of dihalide elimination upon electron attachment to oxalyl chloride and oxalyl bromide, 300-550 K," J.M. Van Doren, K.B. Hogan,* T.M. Miller, and A.A. Viggiano, J. Chem. Phys., 124, 184313 (2006).
"Electron
attachment to POCl3: Measurement and theoretical analysis of rate constants
and branching rations as a function of gas pressure and temperature, electron
temperature, and electron energy," J.M. Van Doren, J.F. Friedman, T.M.
Miller, A.A. Viggiano, S. Denifl, P. Scheier, T.D. Mark, and J. Troe, J. Chem
Phys, 124, 124322 (2006).
“Electron
attachment and detachment: C5F5N and C5HF4N,” J. M. Van Doren, Donna M.
Kerr*, Thomas M. Miller,, A. A. Viggiano, J. Chem. Phys. 123, 114303 (2005).
* Undergraduate Student