Persistence of transition-state structure in chemical reactions driven by fields oscillating in time
journal contributionposted on 10.09.2014 by Galen T. Craven, Thomas Bartsch, Rigoberto Hernandez
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Chemical reactions subjected to time-varying external forces cannot generally be described through a fixed bottleneck near the transition-state barrier or dividing surface. A naive dividing surface attached to the instantaneous, but moving, barrier top also fails to be recrossing-free. We construct a moving dividing surface in phase space over a transition-state trajectory. This surface is recrossing-free for both Hamiltonian and dissipative dynamics. This is confirmed even for strongly anharmonic barriers using simulation. The power of transition-state theory is thereby applicable to chemical reactions and other activated processes even when the bottlenecks are time dependent and move across space.
This work was partially supported by the National Science Foundation through Grant No. NSF- CHE-1112067. Travel between partners was partially supported through the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme FP7/2007-2013/ under REA Grant Agreement No. 294974.
- Mathematical Sciences