Mode-dependent H atom tunneling dynamics of the S 1 phenol is resolved by the simple topographic view of the potential energy surfaces along the conical intersection seam.

Mode-dependent H atom tunneling dynamics of the O-H bond predissociation of the S 1 phenol has been theoretically analyzed. As the tunneling is governed by the complicated multi-dimensional potential energy surfaces that are dynamically shaped by the upper-lying S 1 (ππ*)/S 2 (πσ*) conical intersection, the mode-specific tunneling dynamics of phenol (S 1 ) has been quite formidable to be understood. Herein, we have examined the topography of the potential energy surface along the particular S 1 vibrational mode of interest at the nuclear configurations of the S 1 minimum and S 1 /S 2 conical intersection. The effective adiabatic tunneling barrier experienced by the reactive flux at the particular S 1 vibrational mode excitation is then uniquely determined by the topographic shape of the potential energy surface extended along the conical intersection seam coordinate associated with the particular vibrational mode. The resultant multi-dimensional coupling of the specific vibrational mode to the tunneling coordinate is then reflected in the mode-dependent tunneling rate as well as nonadiabatic transition probability. Remarkably, the mode-specific experimental result of the S 1 phenol tunneling reaction [K. C. Woo and S. K. Kim, J. Phys. Chem. A 123, 1529-1537 (2019)] (in terms of the qualitative and relative mode-dependent dynamic behavior) could be well rationalized by semi-classical calculations based on the mode-specific topography of the effective tunneling barrier, providing the clear conceptual insight that the skewed potential energy surfaces along the conical intersection seam (strongly or weakly coupled to the tunneling reaction coordinate) may dictate the tunneling dynamics in the proximity of the conical intersection.