The surface crossing of bound and unbound electronic states in multidimensional space often gives rise to resonances in the continuum. This situation happens in the πσ*-mediated photodissociation reaction of 2-fluorothioanisole; optically-bright bound S _(1) (ππ*) vibrational states of 2-fluorothioanisole are strongly coupled to the optically-dark S _(2) (πσ*) state, which is repulsive along the S–CH _(3) elongation coordinate. It is revealed here that the reactive flux prepared at such resonances in the continuum bifurcates into two distinct reaction pathways with totally different dynamics in terms of energy disposal and nonadiabatic transition probability. This indicates that the reactive flux in the Franck–Condon region may either undergo nonadiabatic transition funneling through the conical intersection from the upper adiabat, or follow a low-lying adiabatic path, along which multiple dynamic saddle points may be located. Since 2-fluorothioanisole adopts a nonplanar geometry in the S _(1) minimum energy, the quasi-degenerate S _(1) /S _(2) crossing seam in the nonplanar geometry, which lies well below the planar S _(1) /S _(2) conical intersection, is likely responsible for the efficient vibronic coupling, especially in the low S _(1) internal energy region. As the excitation energy increases, bound-to-continuum coupling is facilitated with the aid of intramolecular vibrational redistribution, along many degrees of freedom spanning the large structural volume. This leads to the rapid domination of the continuum character of the reactive flux. This work reports direct and robust experimental observations of the nonadiabatic bifurcation dynamics of the reactive flux occurring at resonances in the continuum of polyatomic molecules.
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