Identifying reactive trajectories using a moving transition state.
A time-dependent no-recrossing dividing surface is shown to lead to a new criterion for identifying reactive trajectories well before they are evolved to infinite time. Numerical dynamics simulations of a dissipative anharmonic two-dimensional system confirm the efficiency of this approach. The results are compared to the standard fixed transition state dividing surface that is well-known to suffer from recrossings and therefore requires trajectories to be evolved over a long time interval before they can reliably be classified as reactive or nonreactive. The moving dividing surface can be used to identify reactive trajectories in harmonic or moderately anharmonic systems with considerably lower numerical effort or even without any simulation at all.
Bartsch
Thomas
T
Center for Nonlinear Science, Georgia Institute of Technology, Atlanta, Georgia 30332-0430, USA.
Uzer
T
T
Moix
Jeremy M
JM
Hernandez
Rigoberto
R
D000465:Algorithms; D002627:Chemistry, Physical / Q000379:methods*; D003198:Computer Simulation; D003201:Computers; D008956:Models, Chemical; D008958:Models, Molecular; D015233:Models, Statistical; D008962:Models, Theoretical; D011336:Probability; D013997:Time Factors