High-resolution millimeter wave spectroscopy and multichannel quantum defect theory of the hyperfine structure in high Rydberg states of molecular hydrogen H2

Experimental and theoretical methodologies have been developed to determine the hyperfine structure of molecular ions from detailed studies of the Rydberg spectrum and have been tested on molecular hydrogen. The hyperfine structure in l=0–3 Rydberg states of H2 located below the X 2Σg+(v+=0,N+=1) ground state of ortho H2+ has been measured in the range of principal quantum number n=50–65 at sub-MHz resolution by millimeter wave spectroscopy following laser excitation to np and nd Rydberg states using a variety of single-photon and multiphoton excitation sequences. The np11, nd11, and the nf10–3 Rydberg states were found to be metastable and to have lifetimes of more than 5 μs beyond n=50. Members of other series, such as the nd12, nd13, and the np10 series, were found to have lifetimes of more than 1 μs. Local perturbations induced by low-n Rydberg states belonging to series converging on rovibrationally excited levels of H2+ reduce the lifetimes in narrow ranges of n values. The hyperfine structure is st...