Chemical Studies of Free Radical Relocalization
Abstract
This project seeks to expand our understanding of the dynamics of combustion intermediates subject to relocalization by a combination of gas-phase laboratory spectroscopy, photochemical studies, and ab initio computations. (1) Spectroscopy. Survey scans between 1800 and 2000 cm-1 of an acetylene/CO discharge, both at room temperature and at 110 K, reveal rich spectra. Students are currently working to assign the lines. Gaps in earlier scans are being filled by means of a new quantum cascade laser. Our apparatus generates stimulated emission in ozone at a previously undetected 5 micron region, but work remains to characterize the relevant dynamics. (2) Photochemistry. Students synthesized an acroleinyl radical precursor (2-bromopropen-3-al), but photochemical studies revealed no interesting chemistry. Studies are continuing, this time starting from commercially available acryloyl chloride (3-chloropropen-3-al). (3) Computations. We developed an optimized interpolation scheme for use with FEMvib, our solver for the vibrational Schrodinger equation on arbitrary potential energy surfaces. This advance greatly expands the usefulness of this resource, which is now available as a public web service (http://islands. sdsu.edu). We completed studies of the propynonyl radicals, now in preparation for publication. New studies of the vibrational manifolds of cyclooctatetraenyl radical and selected hydrogen-transfer pathways in organotransition metal catalysis are underway.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 13, 2015
- Accession Number
- ADA624118
Entities
People
- Andrew L. Cooksy
Organizations
- University of California, San Diego