The 5s2 1S0–5s5p1,3PJ energy intervals in the Cd isoelectronic sequence have been investigated through a semiempirical systematization of recent measurements and through the performance of ab initio multiconfiguration Dirac–Fock calculations. Screening-parameter reductions of the spin–orbit and exchange energies both for the observed data and for the theoretically computed values establish the existence of empirical linearities similar to those exploited earlier for the Be, Mg, and Zn sequences. This permits extrapolative isoelectronic predictions of the relative energies of the 5s5p levels, which can be connected to 5s2 using intersinglet intervals obtained from empirically corrected ab initio calculations. These linearities have also been examined homologously for the Zn, Cd, and Hg sequences, and common relationships have been found that accurately describe all three of these sequences.
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Where available, observed (Ob) and predicted (Pr) values are compared.
Obtained from the fits of Table 3, Eqs. (1)–(6), and c below.
Obtained by summing the corresponding column in Table 1 and the empirically fitted correction 280–1046Z + 42.75Z2.
Tables (4)
Table 1
The Experimental Data Base with Source References, Together with the Results of the Multiconfiguration Dirac–Fock Calculation (in cm−1)
Where available, observed (Ob) and predicted (Pr) values are compared.
Obtained from the fits of Table 3, Eqs. (1)–(6), and c below.
Obtained by summing the corresponding column in Table 1 and the empirically fitted correction 280–1046Z + 42.75Z2.