Rydberg states quantum defect functions

Ross and Jungen (1999) have used differences between ab initio ion-core and Rydberg state potential curves to determine quantum defect functions. Thus the independent quantum defect functions associated with the atom-like Hel(°) and the molecular H 1) are, respectively, ai(R) and ai (R). 

The 3-photon ionization photoelectron spectrum, plotted as the photoelectron signal intensity as a function of the binding energy of the Rydberg states, is shown in Fig. 2. Three series of Rydberg peaks, with quantum defects of 0.93, 0.76, and 0.15 are obtained. From the quantum... 

There are two parameters in the atomic coulomb functions, the effective nuclear charge and the quantum defect. The values of these were taken by Johnson and Rice from available spectral data. The effective atomic charge was adjusted to give the correct ionization potential of the molecule, 9.25 eV, requiring thereby z = 0.8243. The quantum defects of carbon were taken from the appropriate atomic series and were 1.04 for the 5-state and 0.73 for the p-states. It is interesting to compare the calculated molecular quantum defects (i.e., those corresponding to the Johnson-Rice LCAO function) with those which can be obtained from the various benzene Rydberg series.218 The asymptotic form of the elu orbital constructed from s atomic functions is... 

Apart from the electronic structure of the Rydberg states the three-channel quantum defect analysis yields the wave function of the 5dld D2 perturber... 

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