Resonant Tunneling in Chemistry from Quantum Trajectory Base Method
Résumé
Owing to its reactivity enhancing properties, quantum tunneling represents one of the
most crucial effects to account for in order to achieve accurate prediction of rate
constants for numerous chemical processes[1], even at ambient temperature[2]. Over
the years, efficient methods emerged to accurately reproduce quantum tunneling in
approximate atomistic simulations, with much progress being made on assessing the
multidimensional character of the optimal tunneling path[3]. However resonant
tunneling still proves to be a difficult phenomenon to characterize in the aforementioned
methodological framework. In this talk, we present a purely trajectory based[4]
approach of great accuracy and efficiency[5] applied to potential energy profiles subject
to resonant tunneling. The working equations are a set of first order ODEs for a
Hamiltonian in an extended phase space with respect to its classical analog. Trajectory
propagation time enjoys a close relationship with collision lifetime, allowing to directly
recover Smith's quantal time delay[6] at the energy of interest and thus giving further
insight into resonant phenomena[7]. Trajectories describing scattering states with a
reflection probability of nearly unity manifest strong destructive interference patterns,
resulting in a very arduous numerical integration. This is reminiscent of pathologic
numerical behavior encountered by the log-derivative approach in the deep tunneling
regime[8] and constitutes a specific form of the well-known « node problem »
encountered in Bohmian Dynamics[9]. To cope with the node problem, we propose an
efficient semi-analytic scheme allowing trajectories to bypass nodes without significant
loss of accuracy. As a result the method is a robust tool to analyse resonant reactive
scattering.