Nonadiabatic transition paths from quantum jump trajectories

Kavli Affiliate: David T. Limmer

| First 5 Authors: Michelle C. Anderson, Addison J. Schile, David T. Limmer, ,

| Summary:

We present a means of studying rare reactive pathways in open quantum systems
using Transition Path Theory and ensembles of quantum jump trajectories. This
approach allows for elucidation of reactive paths for dissipative, nonadiabatic
dynamics when the system is embedded in a Markovian environment. We detail the
dominant pathways and rates of thermally activated processes, as well as the
relaxation pathways and photoyields following vertical excitation in a minimal
model of a conical intersection. We find that the geometry of the conical
intersection affects the electronic character of the transition state, as
defined through a generalization of a committor function for a thermal barrier
crossing event. Similarly, the geometry changes the mechanism of relaxation
following a vertical excitation. Relaxation in models resulting from small
diabatic coupling proceed through pathways dominated by pure dephasing, while
those with large diabatic coupling proceed through pathways limited by
dissipation. The perspective introduced here for the nonadiabatic dynamics of
open quantum systems generalizes classical notions of reactive paths to
fundamentally quantum mechanical processes.

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