3p-3d Interaction

In an independent particle picture, one has a discrete state, like 3p 3d + interacting with the continnum 3d ef, ep. Configuration interaction mixes the discrete state, which loses its separate existence, in the continnum. The transition moment... 

Is 2s 2p 3s 3p 3d 4s. If the 3d states were truly core states, then one might expect copper to resemble potassium as its atomic configuration is ls 2s 2p 3s 3p 4s The strong differences between copper and potassium in temis of their chemical properties suggest that the 3d states interact strongly with the valence electrons. This is reflected in the energy band structure of copper (figure Al.3.27). 

One should also mention discussions concerning the relevant border between the core and the valence shells. For copper atom, for instance, one may either consider a (19e ) 3s 3p 3d °4s, an (1 le ) 3d °4s or even a (le ) 4s valence shell. In the latter case the core polarizability effects must be treated explicitly. As an extreme case, one might introduce (0e ) pseudopotentials, for a rare gas for instance, which would be very useful to treat molecular interactions and matrix spectroscopy results. Attempts to define Ar (Oe ) pseudopotentials from the virtual MO spectrum of Ar have failed to give relevant intermolecular energies and diatomic extraction appeared to be necessary. ... 

The anisotropy parameter is also strongly altered if Fig. 8 corrections are included. As to "Shadow" autoionization 3s- 4p state in Argon it may be presented rudely as double electron dipole excitations 3p 3d 3p. The interaction with "2 electron-2 hole" excitations is very essential in the continuous spectrum also. Near ns-threshold, this interaction enhances the influence of adjoining many-electron shells, nearly completely compensating the decrease of the ns cross-section because of the spectroscopic factor F. It means, that the calculation leads in fact to the same value of q, as it follows from (8). With increase of (a) the influence of connection with all "2 electron-2 hole" states but those taken into account by E rapidly decrease, so that becomes equal to F s that almost complete compensation of g and F influence at threshold is a consequence of a relation analogous to Word identity in Quantum electrodynamics ) which connects the photon-electron vertex and the electron self-energy part. Being valid for Oi->0, it links in our notations F and q in such a way that the equality between experimental and RPAE cross sections, which leads to (8), must hold. 

Figure 11.3 Incoherent interference control (IIC) scheme and potential energy curves fori, Na2 - Na + Na(3d), Na(4s), Na(3p). In this scheme an (on + a), photon excitation to the continuum interferes with an co2 photon from an initially unpopulated state. Two-photons absorption proceeds from an initial state, 0) (in Na2 it is taken to be the v = 5, 7 = 37 state), via the ]is1) (u = 35, 7 = 36,38) intermediate resonance belonging to the interacting, S /3n electronic states. The oj2 photon couples the continuum to the (initially unpopusf lated) E2) (v = 93, J — 36 or u = 93, 7 = 38) level of the lSll/3ril, electronic state j (Taken from Fig. 1, Ref. [201].). feg...

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