The 3s versus 3p Rydberg state photodissociation dynamics of the ethyl radical

Abstract

The photodissociation dynamics of the ethyl radical following excitation into the 3s and 3p Rydberg states are revisited in a joint experimental and theoretical study. Two different methods to produce the ethyl radical, pyrolysis and in situ photolysis, are employed in order to modify the initial ro-vibrational energy distribution characterizing the ethyl radical beam. H-atom velocity map images following excitation of the radical at 243 nm and at 201 nm are presented and discussed along with ab initio potential energy curves focussing on the bridged C_2v geometry. The reported results show that the dynamics following excitation to the 3s Rydberg state is insensitive to the initial internal energy of the parent radical, in contrast to the dynamics on the 3p Rydberg state, which is strongly modified. The role of the bridged C_2v geometry on both photodynamics is highlighted and discussed.