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Photodissociation spectroscopy of the dysprosium monochloride molecular ion (1508.03025v2)

Published 12 Aug 2015 in physics.chem-ph

Abstract: 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.

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