Ab initio study of H photodetachment from the ethyl radical

Abstract

Minimal energy pathways for hydrogen motion in excited electronic states of C 2H 5 have been studied at the CASSCF and MRCI levels. The calculations reveal that after photoexcitation to the 3s and 3p Rydberg states a proton from the CH 3 fragment slides to the bridging position over the center of the CC bond. In 3s ( 2 2 A′ ) the resulting configuration ( 1 2 A 1 , C 2v) is unstable and dissociates to H and C 2H 4 in the ground electronic states without barrier. All three 3p Rydberg states of C 2H 5 are stable relative to the H splitting, and a rapid proton exchange can occur before the dissociation.