General rule for the ionization behavior of alkyl and 1-alkenylperoxy radicals and the stability of their cations

PHYS 609

Giovanni Meloni, gmeloni@sandia.gov1, Talitha M. Selby, tselby@sandia.gov1, Fabien Goulay2, Stephen R. Leone, srl@berkeley.edu2, David L. Osborn, dlosbor@sandia.gov1, and Craig A. Taatjes, cataatj@ca.sandia.gov1. (1) Combustion Research Facility, Sandia National Laboratories, PO Box 969, Livermore, CA 94551-0969, (2) Departments of Chemistry and Physics, University of California at Berkeley / Lawrence Berkeley National Lab, Berkeley, CA 94720
Organic peroxy radicals are important reaction intermediates in the low-temperature oxidation and photooxidation of hydrocarbons both in the atmosphere and in combustion processes. In particular, alkenylperoxy radicals (R'OO) are intermediates in the oxidation of alkenes. This is one of the central reactions occurring in the photochemical smog formation.

Using a multiplexed time-resolved photoionization mass spectrometer we have measured the photoionization efficiency curves of several alkyl and 1-alkenylperoxy radicals. The experimental results together with computational analysis of the electronic structure properties of the studied molecules lead to the enunciation of a general rule predicting the stability of the peroxy cations.

 

PHYS Poster Session - Computational Spectroscopy and Reaction Dynamics
7:30 PM-10:00 PM, Wednesday, April 9, 2008 Morial Convention Center -- Hall A, Poster

Division of Physical Chemistry

The 235th ACS National Meeting, New Orleans, LA, April 6-10, 2008