Time-dependent quantum wave-packet description of the ¹πσ* photochemistry of phenol

Abstract

The photoinduced hydrogen elimination reaction in phenol via the conical intersections of the dissociative ¹πσ* state with the ¹ππ* state and the electronic ground state has been investigated by time-dependent quantum wave-packet calculations. A model including three intersecting electronic potential-energy surfaces (S₀, ¹πσ*, and ¹ππ*) and two nuclear degrees of freedom (OH stretching and OH torsion) has been constructed on the basis of accurate ab initio multireference electronic-structure data. The electronic population transfer processes at the conical intersections, the branching ratio between the two dissociation channels, and their dependence on the initial vibrational levels have been investigated by photoexciting phenol from different vibrational levels of its ground electronic state. The nonadiabatic transitions between the excited states and the ground state occur on a time scale of a few tens of femtoseconds if the ¹ππ*‐¹πσ* conical intersection is directly accessible, which requires the excitation of at least one quantum of the OH stretching mode in the π1π* state. It is shown that the node structure, which is imposed on the nuclear wave packet by the initial preparation as well as by the transition through the first conical intersection (¹ππ*‐¹πσ*), has a profound effect on the nonadiabatic dynamics at the second conical intersection (¹πσ*‐S₀). These findings suggest that laser control of the photodissociation of phenol via IR mode-specific excitation of vibrational levels in the electronic ground state should be possible.