Spectrum of the autoionizing triplet gerade Rydberg states of H2 and its analysis using multichannel quantum-defect theory.

A new spectrum of the autoionizing triplet states of gerade symmetry of H2 has been recorded from the υ″ = 1–4, N″ = 1–3 rovibrational levels of the metastable c 3Π(u)– state in a supersonic beam. The spectrum consists of overlapping ns and nd Rydberg series with n in the range between 4 and 45 converging to the υ+ = 1–4, N+ = 0–5 levels of the X+ 2Σ(g)+ ground state of H2+. Numerous perturbations caused by s–d and rovibrational channel interactions are revealed in the spectrum and were fully assigned by combining double-resonance experiments and ab initio multichannel quantum-defect theory (MQDT). The energy- and internuclear-distance-dependent eigenquantum-defect parameters of MQDT were derived from available ab initio calculations of the low-lying electronic states of H2 and the ground state of H2(+) and were subsequently refined in a global fit to experimental data. The positions of 552 triplet ns and nd Rydberg levels of H2 (361 of which were measured in the present study) could be reproduced with a root-mean-square deviation of 0.2 cm(–1).