Craven14.pdf (2.02 MB)
0/0

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

Download (2.02 MB)
journal contribution
posted on 10.09.2014 by Galen T. Craven, Thomas Bartsch, Rigoberto Hernandez
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.

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 E

Volume

89

Issue

4

Pages

? - ? (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 Society

Version

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

2014

Notes

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.89.040801

ISSN

1539-3755

Language

en

Exports

Logo branding

Keyword(s)

Exports