Transition state theory femtosecond time scale

Third, there is a time scale for the dying out of the recrossings which lead to the reduction of the rate below that predicted by transition state theory. This flux-flux correlation time scale we find in the reactions we have so far studied to be a few tens of femtoseconds. One can hope to discover, again by molecular dynamics simulation, the microscopic cause and nature of these recrossings. It... 

Zaric and HalF predicted a weakly bound structure and a strongly bound intermediate in the reaction path of the activation of methane with the fragment [Tp Rh(CO)] [Tp = HB(3,5-dimethylpyraz()lyl)5 before oxidative addition. Subsequent studies using (microsecond- to femtosecond-scale) time-resolved IR spectroscopy proved that the second intermediate has a strongly bound r -C,H moiety. Similar structures were determined for the transition states in the C-H activation of methane by the [CpM(PH3)CH3)] (M = Rh, Ir) fragment by ab initio orbital theory methods. ... 

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