Roaming pathways have been seen to pose a threat to accuracy of transition state theory (TST) because naive implementations of TST would not necessarily include their flux. However, more global (and multi-dimensional) dividing surfaces were seen to accommodate the flux of the roaming pathways in earlier work on ketene. Here we provide a fuller picture of this behavior by exploring the structure of the pathways and rates across a continuous range of energies. In addition, we explore the generality of these observations by considering additional unimolecular reactions.

Effects of roaming on reaction kinetics

251st National Meeting (2016)

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