Investigation of ethyl peroxy radical conformers via cavity ringdown spectroscopy of the A-X electronic transition

Patrick Rupper; Erin N Sharp; György Tarczay; Terry A Miller

doi:10.1021/jp066464m

Investigation of ethyl peroxy radical conformers via cavity ringdown spectroscopy of the A-X electronic transition

J Phys Chem A. 2007 Feb 8;111(5):832-40. doi: 10.1021/jp066464m.

Authors

Patrick Rupper¹, Erin N Sharp, György Tarczay, Terry A Miller

Affiliation

¹ Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University, 120 West 18th Avenue, Columbus, Ohio 43210, USA.

PMID: 17266223
DOI: 10.1021/jp066464m

Abstract

Both stable conformers, trans (T) and gauche (G), of the ethyl peroxy radical and its perdeutero analogue have been observed via cavity ringdown spectroscopy (CRDS) of the A2A'-X2A' ' electronic transition in the near-IR. Assignments of specific spectral lines to the electronic transition origin (T00), to observed vibrational hot bands, and to the COO bend and the O-O stretch vibrations are given with the help of equation of motion (EOMIP) quantum chemical calculations. In particular, spectral information for the previously unknown/unassigned T conformer of ethyl peroxy is given in this study for the first time and compared to the data for the previously observed G conformer. The conformer assignment is confirmed by an analysis of the partially resolved rotational structures. The electronic origins for the T and G conformers of C2H5O2 are located at 7362(1) and 7592(1) cm-1, respectively.