Conformer-Specific Tunneling Dynamics Dictated by the Seam Coordinate of the Conical Intersection

The dynamic role of the conical intersection "seam" coordinate has been first revealed in the H fragmentation reaction of ortho(o)-cresol conformers. One of the (3N - 8) dimensional seam coordinates of the S₁(ππ*)/S₂(πσ*) conical intersection has been identified as the CH₃ torsional potential function. The tunneling dynamics of the reactive flux is dictated by its nuclear layout with respect to the CH₃ torsional angle, as the multidimensional tunneling barrier is dynamically shaped along the conical intersection seam. The effective tunneling-barrier weight-averaged over the quantum-mechanical probability along the CH₃ torsional angle perfectly explains the experimental finding: the sharp variation of the tunneling rate ((700-400) ps^-1) with the CH₃ torsional mode excitations within the narrow (0-100 cm^-1) energetic window. The much longer S₁ lifetime of cis compared to trans is ascribed to the higher-lying S₁/S₂ conical intersection of the former. With the use of distinct lifetimes, vibronic bands of each conformer could be completely separated.