Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects

Abstract

AbstractThe photodissociation of phenol is a prototype of the photoinduced hydrogen detachment reaction. The dissociation rates of phenol through the excited S1 state are calculated with the quantum instanton method in full dimensionality. The Arrhenius plot of the rates shows that the quantum tunneling dominates the OH bond dissociation at low temperatures. The degrees of freedom of phenyl ring (C6H5) play extremely important roles in the dissociation of phenol. Fixing the phenyl ring at the equilibrium geometry can only provide reliable rates between 400 K and 800 K. The motions of phenyl ring have an impact on enhancing the dissociation by lowering the free energy barrier. The larger the amplitudes of the phenyl ring motions are, the more the free energy barrier will be reduced. The dissociation rates of C6H5OH are much larger than those of C6H5OD, which is due to the zero‐point energy and entropy effects.