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Photodissociation spectroscopy of the dysprosium monochloride molecular ion
Dunning, A Petrov, A Schowalter, SJ Puri, P Kotochigova, S Hudson, ER
Dunning, A
Petrov, A
Schowalter, SJ
Puri, P
Kotochigova, S
Hudson, ER
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Journal Article
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2015-09-28
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10.1063/1.4931817
Abstract
© 2015 AIP Publishing LLC. We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl<sup>+</sup>. The photodissociation cross section for the photon energy range 35 500 cm<sup>-1</sup> to 47 500 cm<sup>-1</sup> 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<sup>-1</sup>. 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<sup>+</sup> is extremely complex due to the presence of multiple open electronic shells, including the 4f<sup>10</sup> configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy<sup>+</sup> 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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Journal of Chemical Physics
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