THREE AND FOUR CENTER ELIMINATION OF HC1 IN THE MULTIPHOTON DISSOCIATION OF HALOGENATED HYDROCARBONS Page: 27 of 54
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A couple of important conclusions on 4-center elimination can
be readily drawn from our observations. The results on the average
translational energy released to fragments suggest that a large
fraction (> 85%) of the total excess energy is left as internal
excitation of the fragments. This is just the opposite of what we
found in 3-center elimination reactions. A large fraction of the
internal energy should appear as vibrational energy of the CH2CC12
fragment. Of course, the HCl fragments must also be highly
vibrationally excited. In fact, in a similar unimolecular reaction
involving elimination of HF from CH3CF3, Berry and Pimentel13
observed laser emission from the vibrationally excited HF. Our
results also indicate that in a 4-center elimination, the critical
configuration should not be modelled by a BCl molecule loosely
coupled to a CH2CC12 molecule, but rather by a distorted CH3CC13
molecule with a lot of stored potential energy and a partial bond
formed between a Cl and H atom. This picture resembles closely
models for the critical configuration used by Setser et al.12 for
similar reactions.
In our present investigation, a special case is provided by
CHC1CF2. The 3-center elimination from this molecules does not seem
to have any appreciable back reaction barrier in the exit channel,
and the translational energy distribution of the fragments is very
much like the one observed in halogen atom eliminations. This
is a result similar to the conclusion of Kim and Setser12 about the
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Sudbo, Aa. S.; Schulz, P.A.; Shen, Y.R. & Lee, Y.T. THREE AND FOUR CENTER ELIMINATION OF HC1 IN THE MULTIPHOTON DISSOCIATION OF HALOGENATED HYDROCARBONS, article, April 1, 1978; Berkeley, California. (https://digital.library.unt.edu/ark:/67531/metadc840434/m1/27/: accessed April 23, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.