Abstract
Abstract Two striking examples of Rydberg/ion-pair state coupling have been observed in the spectrum of I 2 in the regions 62500–64000 and 56500–59500 cm −1 . The coupling is of intermediate strength and the (2+1) REMPI spectra of the resonant Ry ← X transitions have ion-pair satellites around each Rydberg vibrational level from which they have borrowed intensity. The Rydberg states are identified as the [ 2 Π 3 2 ] c 7 s ;1 g and [ 2 Π 3 2 ] c 5 d ; 2 g and the ion-pair states as the β1g and D′2g. Curve crossings occur close to the ν ′ = 532 level of the β state and ν ′ = 311 of the D′ state respectively. The spectra are modelled by solving the two-state coupling problem in a diabatic basis and in order to deduce approximate values of the coupling matrix elements, extrapolations of the known portions of the potential energy curves of the β1g and D′2g ion-pair states are necessary. The diagnostic value of the magnitude of the electronic part of Rydberg/ion-pair coupling matrix elements in probing the electronic configuration of ion-pair states at short range is discussed.
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