Photodissociation spectroscopy of the dysprosium monochloride molecular ion

We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl(+). The photodissociation cross section for the photon energy range 35,500 cm(-1) to 47,500 cm(-1) is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43,000 cm(-1). The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl(+) is extremely complex due to the presence of multiple open electronic shells, including the 4f(10) configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy(+) ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.