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26,000 and ca. 46,000 cm -l above the ground-state ion energies, respectively; in contrast, the first similar excited state of Na +, the Na+(2pS3s 2p) state, lies ca. 265,000 crn-1 above the ground state. Calculations of Cu+-Ar versus Na+-Ar potential curves by Bauschlicher et al. 4~are consistent with this idea, since the D e value for Cu+-Ar is 3270 cm -1, nearly three times greater than that of Na+-Ar. 86/~. 53/~. The ab initio calculations show that there is important sdo hybridization in Cu+-Ar and Ar-Cu +Ar bonding.
73 Also, if the Ar atom can get close to the Sit (3s)" core, it may encounter a net positive charge of more than + 1, because it is approaching along the Si(3pn) nodal axis. The rotational band contour simulations were much more sensitive to the AB values than to absolute B v" values, 44 and the true R e value for Si(3s23p4s 3pj). Ar(3H) may be quite small. 8/~ and/or an effective charge greater than +1 would appear to be required to adequately rationalize the 2100-cm -l bond strength with any sort of Rydberg electrostatic bonding arguments.
RG(IFI1) states. The concept of back-polarization will be discussed further in the next section on Rydberg-type states. There are two examples where 1II1 states are not very strongly bound: CaAr and SrAr. The bond strengths, 134 and 136 crn-1, respectively, are substantially smaller than that of their lighter counterpart, MgAr(llIl), which has a D e of 368 crn-1. There may be two reasons for this. The Ca(4s) and Sr(5s) cores will be much larger than that of Mg(3s) [in contrast to the Zn(4s) and Cd(5s) cores, which are smallerowing to the d-shell shielding effect], and repulsion may just set in at larger internuclear distances.