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Persistence of transition-state structure in chemical reactions driven by fields oscillating in time
Galen T Craven1, Thomas Bartsch2, Rigoberto Hernandez1
1Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
Abstract:
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.
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