High-resolution spectroscopy and quantum-defect model for the gerade triplet np and nf Rydberg states of He2
Abstract
Photoionization spectra and Rydberg-state-resolved threshold-ionization spectra of the gerade triplet np Rydberg states of 4He2 located in the vicinity of the X^+ ^2Σ _u^+ (v^+=0) ionization threshold were recorded from the 2sσ a ^3Σ _u^+ metastable state. An accuracy of 0.01 cm-1 was achieved for the experimental term values of the observed Rydberg states. The data were combined with spectroscopic data on low-lying triplet np and nf Rydberg states from the literature to derive energy- and internuclear-distance-dependent eigenquantum-defect parameters of multichannel quantum-defect theory (MQDT). The MQDT calculations reproduce the experimental data within their experimental uncertainties and enabled the derivation of potential-energy curves for the lowest triplet p Rydberg states (n = 2-5) of He2. The eigenquantum-defect parameters describing the p -f interaction were found to be larger than 0.002 at the energies corresponding to the high-n Rydberg states, so that the p -f interaction plays an important role in the autoionization dynamics of np Rydberg states with v+ = 0. By extrapolating the experimental term values of triplet np Rydberg states of 4He2 in the range of principal quantum number n between 87 and 110, the positions of the (v+ = 0, N+ = 3) and (v+ = 0, N+ = 5) levels of the ground state of 4He_2^+ were determined to lie 70.937(3) cm-1 and 198.369(6) cm-1, respectively, above the (v+ = 0, N+ = 1) ground rotational level.
- Publication:
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Journal of Chemical Physics
- Pub Date:
- February 2014
- DOI:
- Bibcode:
- 2014JChPh.140f4304S