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7. Conclusion
˜
˜
In this work, we report the A-X absorption spectra of
cyclopentyl, cyclohexyl, and cyclohexyl-d11 peroxy radicals, as
measured by ambient temperature cavity ringdown spectroscopy.
For all three species, the spectra obtained are consistent with
calculated predictions for the gauche conformers, while calcula-
tions do not permit any band to be uniquely assignable to a
cis-conformer of either peroxy, although plausible assignments
are discussed. Although some of the cis-conformers would be
expected to be observable on the basis of their Boltzmann
populations, overlap of their band origins with vibrational
features of the gauche forms and smaller oscillator strengths
are viable explanations for the ambiguity of their assignments
or lack of observation. The spectrum of cyclopentyl peroxy is
well explained by a pair of coinciding gauche conformers,
perhaps with contributions from the C conformer in the COO
bend region. The spectrum of cyclohexyl peroxy is most clearly
interpreted as the superposition of two gauche conformers, with
axial and equatorial ring substitution, respectively. Shapes of
the electronic origin bands are well reproduced by hot band
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Acknowledgment. We acknowledge the financial support of
this work by the DOE via Grant DE-FG02-01ER14172 and a
grant of computer time from the Ohio Supercomputer Center.
We gratefully acknowledge Prof. John F. Stanton (University
of Texas) for useful discussion and independent Franck-Condon
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