Chemical reactions induced by oscillating external fields in weak thermal environments

Abstract

Chemical reaction rates must increasingly be determined in systems that evolve under the control of external stimuli. In these systems, when a reactant population is induced to cross an energy barrier through forcing from a temporally varying external field, the transition state that the reaction must pass through during the transformation from reactant to product is no longer a fixed geometric structure, but is instead time-dependent. For a periodically forced model reaction, we develop a recrossing-free dividing surface that is attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T. Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for single-mode sinusoidal driving, the stability of the time-varying transition state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R. Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous work to the case of multi-mode driving waveforms. Excellent agreement is observed between the rates predicted by stability analysis and rates obtained through numerical calculation of the reactive flux. We also show that the optimal dividing surface and the resulting reaction rate for a reactive system driven by weak thermal noise can be approximated well using the transition state geometry of the underlying deterministic system. This agreement persists as long as the thermal driving strength is less than the order of that of the periodic driving. The power of this result is its simplicity. The surprising accuracy of the time-dependent noise-free geometry for obtaining transition state theory rates in chemical reactions driven by periodic fields reveals the dynamics without requiring the cost of brute-force calculations.

References in corpus (24)

• Equality connecting energy dissipation with violation of fluctuation-response relation
• Wigner's Dynamical Transition State Theory in Phase Space: Classical and Quantum
• Surmounting Oscillating Barriers
• The Transition State in a Noisy Environment
• Microcanonical rates, gap times, and phase space dividing surfaces
• Noise-Activated Escape from a Sloshing Potential Well
• Surmounting Oscillating Barriers: Path-integral approach for Weak Noise
• Stochastic Transition States: Reaction Geometry amidst Noise
• Limit cycles, complex Floquet multipliers and intrinsic noise
• Simple models for two-dimensional tunable colloidal crystals in rotating ac electric fields
• Identifying reactive trajectories using a moving transition state
• Phase space geometry and reaction dynamics near index two saddles
• Generalized Floquet theory: application to dynamical systems with memory and Bloch's theorem for nonlocal potentials
• Bifurcations of transition states: Morse bifurcations
• Activated escape over oscillating barriers: The case of many dimensions
• Chaotic Dynamics in Multidimensional Transition States
• Activated escape of periodically modulated systems
• Transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields
• Persistence of transition state structure in chemical reactions driven by fields oscillating in time
• Reaction dynamics through kinetic transition states
• Reaction rate calculation with time-dependent invariant manifolds
• Measuring disorder in irreversible decay processes
• Transition State Theory for dissipative systems without a dividing surface
• Microscopic description of the equality between violation of fluctuation-dissipation relation and energy dissipation

Cited by in corpus (12)

• Electron transfer across a thermal gradient
• Obtaining time-dependent multi-dimensional dividing surfaces using Lagrangian descriptors
• Chemical dynamics between wells across a time-dependent barrier: Self-similarity in the Lagrangian descriptor and reactive basins
• Invariant Manifolds and Rate Constants in Driven Chemical Reactions
• Energy transport between heat baths with oscillating temperatures
• Neural network approach to time-dependent dividing surfaces in classical reaction dynamics
• Phase-space resolved rates in driven multidimensional chemical reactions
• 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
• Controlling reaction dynamics in chemical model systems through external driving
• 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