Matthew Sprague

B.A., Physics, B.S., Chemistry, Ithaca College, 2005
Fifth-year graduate student

We are studying the chemical kinetics of atmospherically relevant reactions using infrared cavity ringdown spectroscopy (IR-CRDS). The main advantage to using IR-CRDS is sensitivity, as we can study reaction kinetics at very low concentrations, or of molecules that are typically weak IR absorbers. Our current study is of the reaction of butoxy radical with O2, which is part of a reaction cycle that produces NOx.

We are also interested in studying HOONO, a nitric acid isomer produced from the reaction NO2 + OH. HOONO has a short lifetime, and therefore does not act as a sink of NO2. The lowest energy isomer of HOONO is a planar geometry containing an internal hydrogen bond. Torsional excitation in HOONO breaks this hydrogen bond, causing a shift in the OH stretch frequency. In collaboration with Professor Anne McCoy (Ohio State), we have computed potential energy surfaces to model the coupling between the torsional modes and OH stretch mode of HOONO. The simulated OH stretch spectrum will allow us to refine our interpretation of the previously acquired CRDS measurements.

Publications

  1. McCoy, A.B., M.K. Sprague, and M. Okumura, "The role of torsion/torsion coupling in the vibrational spectrum of cis-cis HOONO," J. Phys. Chem. A, in press (2009).

  2. DeTuri, V.F. and M.K. Sprague. "Energetic and geometric insights of methoxide in methanol CH3O-(CH3OH)n, for n = 1-21," in preparation.

  3. Garland, E.R., A.K. Mollner, M.K. Sprague, C. Morrell, B.D. Bean, M. Okumura, and S.P. Sander. "Kinetics of Butoxy and Pentoxy Radicals and Detection of Isomerization Products using Pulsed Laser Photolysis - Cavity Ringdown Spectroscopy," in preparation.

  4. Mollner, A.K., L. Feng, M.K. Sprague, S.P. Sander, D.B. Milligan, W.J. Bloss, R.A. Harley, P.T. Martien, A.B. McCoy, and M. Okumura. "Rate of gas phase association of hydroxyl radical and nitrogen dioxide," submitted to Science.

  5. Dentinger, P.M., B.A. Simmons, E. Cruz, and M. Sprague. “DNA-Mediated Delivery of Lipophilic Molecules via Hybridization to DNA-Based Vesicular Aggregates,” Langmuir 22 (2006): 2935-2937.

Funding

National Defense Science and Engineering Graduate Fellowship, 2006-2009

Extracurricular Interests

Music (trumpet), computer repair, video games, board games, NFL Football (Buffalo Bills)