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Title: Chemical reactions induced by oscillating external fields in weak thermal environments
Authors: Craven, Galen T.
Bartsch, Thomas
Hernandez, Rigoberto
Issue Date: 2015
Publisher: © American Institute of Physics
Citation: CRAVEN, G.T., BARTSCH, T. and HERNANDEZ, R., 2015. Chemical reactions induced by oscillating external fields in weak thermal environments. Journal of Chemical Physics, 142, 074108.
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.
Description: The following article appeared in Journal of Chemical Physics and may be found at: http://dx.doi.org/10.1063/1.4907590) Copyright (2015) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
Sponsor: This work has been partially supported by the Air Force Office of Scientific Research through Grant No. FA9550-12-1-0483. 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.
Version: Published
DOI: 10.1063/1.4907590
URI: https://dspace.lboro.ac.uk/2134/16956
Publisher Link: http://dx.doi.org/10.1063/1.4907590
ISSN: 1089-7690
Appears in Collections:Published Articles (Maths)

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