Journal of Physical Chemistry A, Vol.123, No.16, 3535-3542, 2019
Spectrum of Field-Ionized Triplet Gerade Rydberg States of H-2 and Comparison to Multichannel Quantum-Defect Theory
A spectrum of field-ionized triplet Rydberg states of gerade symmetry H-2 has been measured, excited from the v '' = 0, N '' = 1-3 rovibrational levels of the metastable c(3)Pi(-)(u)2p pi state in a 6 keV fast molecular beam. The field-ionized spectrum is kinetic energy labeled in order to separate it from the well-studied v(+) >= 1 autoionization spectrum. The spectrum consists of both ns and nd Rydberg series with n between 10 and 28 converging to the v(+) = 0, N+ = 1-3 levels of the X+ (2)Sigma(+)(g) ground state of H-2(+). Transitions with changes in vibration and/or rotation are also identified. The spectral positions of 59 transitions in the field ionization spectrum are identified and assigned quantum numbers using the predictions of multichannel quantum-defect theory (MQDT). The transition energies and subsequent effective quantum defects are compared between the experiment and theory. Most of the observed transitions, within the experimental uncertainty of 0.2 cm(-1), agree with the energies predicted by MQDT.