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Persistence of transition-state structure in chemical reactions driven by fields oscillating in time
journal contribution
posted on 2014-09-10, 10:26 authored by Galen T. Craven, Thomas BartschThomas Bartsch, Rigoberto HernandezChemical 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.
Funding
This work was partially supported by the National Science Foundation through Grant No. NSF- CHE-1112067. 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.
History
School
- Science
Department
- Mathematical Sciences
Published in
PHYSICAL REVIEW EVolume
89Issue
4Pages
? - ? (5)Citation
CRAVEN, G.T., BARTSCH, T. and HERNANDEZ, R., 2014. Persistence of transition-state structure in chemical reactions driven by fields oscillating in time. Physical Review E, 89 (4), 5pp.Publisher
© American Physical SocietyVersion
- VoR (Version of Record)
Publisher statement
This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/Publication date
2014Notes
This article was published in the journal, Physical Review E [© American Physical Society] and the definitive version is also available at: http://dx.doi.org/10.1103/PhysRevE.89.040801ISSN
1539-3755Publisher version
Language
- en