Control of Nonadiabatic Passage through a Conical Intersection by a Dynamic Resonance Academic Article uri icon

abstract

  • Non-adiabatic processes, dominated by dynamic passage of reactive fluxes through conical intersections (CIs) are appealing means for manipulating reaction paths, particularly via initial vibrational preparation. Nevertheless, obtaining direct experimental evidence whether specific mode excitation affects the passage at the CI is challenging, requiring well resolved time- or frequency-domain experiments. Here promotion of methylamine-d2 (CH3ND2) molecules, to spectral-resolved rovibronic states on the excited S1 potential energy surface, coupled with sensitive D photofragment probing, allowed to follow the N-D bond fission dynamics. The branching ratios between slow and fast D photofragments, and the internal energies of the CH3ND( ) photofragments confirm correlated anomalies for predissociation initiated from specific rovibronic states. These anomalies reflect existence of a dynamic resonance that strongly depends on the energy of the initially excited rovibronic states, the evolving vibrational mode on the repulsive S1 part during N-D bond elongation, and the manipulated passage through the CI that leads to CH3ND radicals excited with C-N-D bending. This resonance plays an important role in the bifurcation dynamics at the CI and can be foreseen to exist in other photoinitiated processes and to control their outcome.

publication date

  • January 1, 2016