Control of Nonadiabatic Passage through a Conical Intersection by a Dynamic Resonance.
Nonadiabatic processes, dominated by dynamic passage of reactive fluxes through conical intersections (CIs), are considered to be appealing means for manipulating reaction paths, particularly via initial vibrational preparation. Nevertheless, obtaining direct experimental evidence of 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 to sensitive D photofragment probing, allowed us to follow the N-D bond fission dynamics. The branching ratios between slow and fast D photofragments and the internal energies of the CH3ND(X̃) photofragments confirm correlated anomalies for predissociation initiated from specific rovibronic states. These anomalies reflect the 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.
Department of Physics, Ben-Gurion University of the Negev , Beer-Sheva 84105, Israel.
Michael
M
Epshtein
Department of Physics, Ben-Gurion University of the Negev , Beer-Sheva 84105, Israel.
Yair
Y
Yifrach
Department of Physics, Ben-Gurion University of the Negev , Beer-Sheva 84105, Israel.
Alexander
A
Portnov
Department of Physics, Ben-Gurion University of the Negev , Beer-Sheva 84105, Israel.
Ilana
I
Bar