Energy pattern, charge-transfer transitions

All of the calculations described here use local functionals that do not include exact exchange. The best choice of functional for calculating MCD spectra is still an open question. In our experience, the MCD parameters produced with different local functionals do not vary much (83). The exception to this rule is functionals that are asymptotically correct. Asymptotically correct functionals tend to give excitation energies that differ from those produced by standard local functionals, particularly for Rydberg and charge-transfer transitions. The MCD parameters produced by asymptotically correct functionals tend to follow a similar pattern when compared with results of other local functionals. A few studies have considered hybrid functionals (42,43). This work found that hybrid functionals were superior in some applications. More work in this area is needed. 

This observed pattern of charge transfer and switching processes is consistent with the vertical-transition model (Franck-Condon principle) as discussed by Bearman et al. (1976), who interpreted the cross sections for ionic excitation in low-energy charge-transfer collision between HeJ and some diatomic neutrals. In analogy to that, in the cases of KrJ reactions, it is not the total recombination energy RE(KrJ) = 12.85 eV that is available, but only the effective recombination energy Reeff(KrJ) = 11.91 eV, which is determined, as shown in Fig. 6, by the vertical transition from KrJ to the repulsive state of JCr-Kr at the equilibrium distance f o(Kr2 ) ... 

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