Investigation of ethyl peroxy radical conformers via cavity ringdown spectroscopy of the Ã-X̃ electronic transition

Patrick Rupper, Erin N. Sharp, G. Tarczay, Terry A. Miller

Research output: Contribution to journalArticle

26 Citations (Scopus)

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 Ã2A′-X̃ 2A″ electronic transition in the near-IR. Assignments of specific spectral lines to the electronic transition origin (Too), 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 C2H 5O2 are located at 7362(1) and 7592(1) cm-1, respectively.

Original languageEnglish
Pages (from-to)832-840
Number of pages9
JournalJournal of Physical Chemistry A
Volume111
Issue number5
DOIs
Publication statusPublished - Feb 8 2007

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Equations of motion
Spectroscopy
cavities
electronics
spectroscopy
line spectra
equations of motion
analogs
vibration
carboxyl radical

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Investigation of ethyl peroxy radical conformers via cavity ringdown spectroscopy of the Ã-X̃ electronic transition. / Rupper, Patrick; Sharp, Erin N.; Tarczay, G.; Miller, Terry A.

In: Journal of Physical Chemistry A, Vol. 111, No. 5, 08.02.2007, p. 832-840.

Research output: Contribution to journalArticle

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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 {\~A}2A′-X̃ 2A″ electronic transition in the near-IR. Assignments of specific spectral lines to the electronic transition origin (Too), 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 C2H 5O2 are located at 7362(1) and 7592(1) cm-1, respectively.",
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