Persistence of transition-state structure in chemical reactions driven by fields oscillating in time.
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.
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
Galen T
GT
Craven
Department of Mathematical Sciences, Loughborough University, Loughborough LE11 3TU, United Kingdom.
Thomas
T
Bartsch
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
Rigoberto
R
Hernandez