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

Phys Rev E Stat Nonlin Soft Matter Phys. 2014 Apr;89(4):040801. doi: 10.1103/PhysRevE.89.040801. Epub 2014 Apr 28.

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.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.