Vibrational spectroscopy of Xe+2 via pulsed field ionization

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Abstract
Delayed, pulsed field ionization of extremely high‐n Rydberg states has been used in combination with a high‐resolution vacuum ultraviolet radiation source to measure the vibrationally resolved spectra of the first three bound states of Xe+2. For the ground state of the ion (A 2Σ+u), a long progression beginning at v+=56 was observed which included isotopically resolved energy levels. The spectroscopic parameters obtained from a fit of the data to anharmonic oscillator energy levels are reported. The resulting Xe2 ionization potential is somewhat higher than previously reported. Several vibrations of the first excited state (B 2Π(3/2)g) were observed near 97 000 cm−1. An absolute vibrational assignment was not possible due to an unusual alternation of intensities. Nevertheless, a lower bound on the binding energy and an estimated vibrational frequency are reported. For the C 2Π(3/2)u state, the v+=0–2 vibrational levels were observed with an intensity distribution consistent with the weakly bound nature of this state. The derived binding energy and vibrational frequency for the C 2Π(3/2)u state are reported.