Persistence of transition state structure in chemical reactions driven by fields oscillating in time

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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• Transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields
• Invariant Manifolds and Rate Constants in Driven Chemical Reactions
• Neural network approach to time-dependent dividing surfaces in classical reaction dynamics
• Transition State Theory for solvated reactions beyond recrossing-free dividing surfaces
• Neural network approach for the dynamics on the normally hyperbolic invariant manifold of periodically driven systems
• Variational principle for the determination of unstable periodic orbits and instanton trajectories at saddle points
• Dynamics and bifurcations on the normally hyperbolic invariant manifold of a periodically driven system with rank-1 saddle