REACTION DYNAMICS OF THE BROMINE-BROMOFORM COMPLEX IN SOLUTION
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Publisher:Ohio State University
We have followed the evolution of the bromine species that arise from the photolysis of bromoform in the condensed phase. Solvent caging promotes the formation of iso-bromoform (CHBr$_2$-Br), which can then release a Br atom by breaking the newly formed Br-Br bond. This ejected Br can form a van der Waals complex (Br-CHBr$_3$) with a nearby un-photolyzed bromoform molecule, which is stable during our 1 ns time-window. Using the van der Waals complex as a reservoir for Br atoms, we now proceed to drive hydrogen abstraction from CHBr$_3$ by Br. Estimates indicate that the barrier to this reaction is a few thousand wavenumbers. Our goal is to introduce excitation into the C-H stretching motion of a nearby solvent CHBr$_3$ to access the activated complex region of the bimolecular potential energy surface.
Author Institution: The University of Wisconsin-Madison, Department of Chemistry, 1101 University Avenue, Madison, WI 53706
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