Rotational line strengths for ionization are calculated assuming only s partial waves. Rotational band contours are then constructed by broadening each rotational line with a known instrumental line shape. This technique is applied to HF and DF, and reproduces the experimental results well, allowing an accurate value of the spin‐orbit coupling constant to be extracted from experiment. The value of − 290 ± 10 cm−1 agrees with previous Hartree‐Fock calculations. The ionization potentials (16.044 ± 0.003 eV for HF, 16.058 ± 0.003 eV for DF) are obtained with an accuracy one order of magnitude better than the experimental resolution, and there is some evidence for an electronic isotope shift.

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