1
96
PARKER ET AL.
bonding to the O atom of IIC and these are connected
to products via saddle points on the minimum energy
paths. The third involves hydrogen bonding to the N
atom of IIC. One of these (Complex 5) can proceed
through subthreshold saddle point TS1 to transfer the
tertiary hydrogen atom of IIC to hydroxyl radical. Con-
ventional TST is employed to compute the rate con-
stant for this reaction in the T = 200–350 K range, and
with slight downward adjustment of barrier heights by
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−1
2.37 kJ mol , theory reproduces experiment within
13. Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert,
S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.;
Matsunaga, N.; Nguyen, K. A.; Su, S. J.; Windus, T.
L.; Dupuis, M.; Montgomery, J. A. J Comput Chem
the uncertainty. There is a small contribution to the to-
tal reaction occurring by hydrogen atom transfer from
the methyl groups. The theoretical rate constants pro-
vide a basis for extrapolating the laboratory data across
the range of temperature available in the troposphere.
No major products of this reaction were observed; only
acetic acid and acetamide were observed as minor re-
action products. The tropospheric lifetime of IIC has
an upper bound of 6.0 days.
1993, 14, 1347–1363.
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SUPPORTING INFORMATION
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Supporting information to this article is available at
www.interscience.wiley.com. This information con-
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frequencies, and rotational constants for all species
listed in Table II.
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We thank Midwest Research Institute for support of this
work. We thank Dr. Mike Schmidt of Iowa State Univer-
sity for a helpful discussion. We thank the reviewers of the
manuscript for constructive criticisms that were helpful in
our revisions.
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International Journal of Chemical Kinetics DOI 10.1002/kin