Spectrum of Field-Ionized Triplet Gerade Rydberg States of H2 and Comparison to Multichannel Quantum-Defect Theory.

Abstract

A spectrum of field-ionized triplet Rydberg states of gerade symmetry H2 has been measured, excited from the υ″ = 0, N″ = 1-3 rovibrational levels of the metastable c3Πu-2pπ 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 υ+ ≥ 1 autoionization spectrum. The spectrum consists of both ns and nd Rydberg series with n between 10 and 28 converging to the υ+ = 0, N+ = 1-3 levels of the X+ 2Σg+ ground state of H2+. 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.