Double resonance spectroscopy via the EF 1 ⌺ g + , EF Ј =6,JЈ state has been used to probe the rovibrational structure of the ungerade double-well BЉB 1 ⌺ u + state of H 2 . Transitions to the BЉB 1 ⌺ u + , B = 17− 35, J =0−4 levels of the outer-well and to the B Љ B = 46− 50, J =0−4 levels of the combined inner and outer wells above the barrier have been recorded by detecting both molecular and atomic ion production as a function of energy by using a time of flight mass spectrometer. Theoretical energy calculations incorporating the most recent potential curves have been used to aid in the assignment of observed transitions. Over 70 new rovibrational term energies are reported. Where comparisons are possible, good agreement is observed between the experimental measurements reported here and those of previous measurements. While significant perturbations are observed in the energy region above the double-well barrier, assignments to states with dominant inner and outer-well characteristics can still be made. Distinct dynamical behaviors of the levels below, at, and above the barrier have also been observed.
The autoionizing (X X~) gf, 9f, and 10f, v =1 states of N2 have been studied by using doubleresonance ionization spectroscopy via numerous rotational levels of the a 'II~, v'=5 state. These nf states lie in a complex region of the spectrum that also contains transitions to high vibrational levels of the b' 'X"+ valence state and Rydberg states that converge to the X X~, A II",and 8 X"+ states of the ion. A long-range interaction model, which is based on the interaction of the Rydberg electron with the polarizability and quadrupole moment of the N2+ ion core, has been used to intepret the f-state structure and to identify the extent of perturbations due to interactions with nearby states. A generalized least-squares fit of the model to the energies of the unperturbed Sf state yields an effective quadrupole moment of (3.2+0. 1)eao and an isotropic polarizability of (16.1+0.4)ao for the X X~, U+ =1 state of the ion. In addition, a new state that is observed to perturb the 9f, v = 1 state is tentatively identified as the previously unobserved (A H")3dm '6", u =2 state. The results presented here complete the interpretation of the single-photon absorption spectrum of N2 from the first ionization potential at -125 667 to -126 850 cm
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