Dissociation of deuteromethane following carbon1score ionization

Abstract

Energy-resolved electron-ion coincidence spectra of the deuteromethane molecule were measured following ionization by narrow-band synchrotron radiation. The ion mass spectra were recorded in coincidence with the outer and inner valence photoelectrons and with the normal Auger electrons from the decay of the carbon $1s$ core hole. Complementary noncoincidence ion mass spectra were measured below and above the C $1s$ threshold. The fragmentation patterns of the singly and doubly ionized deuteromethane under different ionization conditions are examined. Carbon core ionization is shown to open new photodissociation pathways not available in the valence ionization photon energy regime. With the aid of ab initio quantum chemistry calculations, a two-step model of the dissociation following core ionization is proposed, showing a good agreement with the experimental findings.