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.

References in corpus (8)

• Diamondoid Molecules
• The Transition State in a Noisy Environment
• Stochastic Transition States: Reaction Geometry amidst Noise
• Simple models for two-dimensional tunable colloidal crystals in rotating ac electric fields
• Identifying reactive trajectories using a moving transition state
• Chaotic Dynamics in Multidimensional Transition States
• Reaction rate calculation with time-dependent invariant manifolds
• Transition State Theory for dissipative systems without a dividing surface

Cited by in corpus (6)

• Electron transfer across a thermal gradient
• Chemical reactions induced by oscillating external fields in weak thermal environments
• 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 for the dynamics on the normally hyperbolic invariant manifold of periodically driven systems
• Dynamics and bifurcations on the normally hyperbolic invariant manifold of a periodically driven system with rank-1 saddle