posted on 2013-08-15, 00:00authored byKeith
A. Freel, Michael N. Sullivan, J. Park, M. C. Lin, Michael C. Heaven
The
visible absorption bands of the phenylperoxy radical in the
gas phase have been investigated using cavity ring-down spectroscopy.
Jet-cooling was used to reduce the spectral congestion. Structured
spectra spanning the range from 17 500 to 19 000 cm–1 are reported for the first time. Analyses of these
data have been guided by the results from time-dependent density functional
calculations. The observed spectrum was found to be dominated by the
bands of the B̃2A″–X̃2A″ transition. An analysis of the rotational contour for the
origin band yielded a homogeneous line width of 2.2 cm–1, corresponding to a decay rate of 4.1 × 1011 s–1. The results provide a rationale for the lack of
structure in room temperature spectra that have been previously attributed
to phenylperoxy. They also indicate that the lower energy region of
the spectrum may show resolvable structure at room temperature. If
so, this would provide a more definitive signature for monitoring
phenylperoxy in kinetic measurements.