Nonadiabatic transition-state theory: A Monte Carlo Study of competing bond fission processes in bromoacetyl chloride
Publication date
2001Author
Marks, Alison J.Keyword
Reaction KineticsMorse Potential
Organic Compounds
Potential Energy Surfaces
Monte Carlo Methods
Dissociation
Peer-Reviewed
YesOpen Access status
closedAccess
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Nonadiabatic Monte Carlo transition-state theory is used to explore competing C¿Cl and C¿Br bond fission processes in a simple model of 1[n,pi*(CO)] photoexcited bromoacetyl chloride. Morse potentials are used to represent bond stretching coordinates, and the positions and magnitudes of nonadiabatic coupling between excited state potentials are modeled using ab initio data. The main effect of nonadiabaticity is to favor C¿Cl fission over C¿Br, despite a larger barrier to C¿Cl dissociation. The absolute values of the rate constants are smaller than observed experimentally, but the calculated branching ratios are close to the experimental value. For C¿Cl fission, it is shown that the minimum energy crossing point is not sufficient to describe the rate constant, suggesting that care must be taken when using alternative models which make this assumption.Version
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Marks, A.J. (2001). Nonadiabatic transition-state theory: A Monte Carlo Study of competing bond fission processes in bromoacetyl chloride. Journal of Chemical Physics. Vol. 114, No. 1700.Link to Version of Record
https://doi.org/10.1063/1.1333702Type
Articleae974a485f413a2113503eed53cd6c53
https://doi.org/10.1063/1.1333702