Binding energy jellium

The dominant contributions to the binding energy per electron of jellium can be written in the form... 

Clusters are studied in several forms. A study of the ionization energy and electron affinity of a metal cluster in the stabilized jellium model was recently performed by Sidl et al. [83]. A strictly variational procedure for cluster embedding, based on the extended subspace approach, has been presented by Gutdeutsch, Birkenheuer, and R6sch[84]. Initially used with the tight-binding model Hamiltonians, it has the potential to be extended to real Hamiltonians. 

Assume that the binding curves for the asymptotic fragments are available and have been used to determine the relevant parameters (7>ab> ab> ab)> (Das, Kas. l As) (Dj,s, bs. bs)- The parameters for the interaction with jellium, (Dah, ah. ah) and (Dbh, bh. bh). are not adjustable, being determined by the SCF-LD values. Thus, the remaining variables in the PES, the so-called Sato parameters, Aab>A s, and A s, are undetermined and available for flexible representation of the full molecule-solid reactive PES. We consider the effect of these on the PES later. At this point, we do want to emphasize that the basic physics and chemistry— (1) interactions with localized and delocalized metal electrons and (2) nonadditive chemical bonding—are correct. We should also note that the representation of an interaction in metals in terms of an embedding function (in jellium) plus two-body terms is identical in spirit to the embedded atom method (EAM) (Daw and Baskes 1984, 1988). The distinction here is that we do not use the EAM for the A-B interaction and explicitly incorporated nonadditive energies via the LEPS prescription, both of which are important for the accurate representation of the reactive PES. 

Clearly, the validity of this approach will depend on the nature of the atoms involved. From the standpoint of a chemist, the obvious flaw of the jellium model is its total neglect of ionic structure. The model requires that the valence electrons should be strongly delocalised. This can only be true for certain metals which are very good conductors. It is also favoured if the ionic background is easily perturbed, in which case electronic single particle energies determine the structure. Finally, it tends to apply better when the wavefunctions have s character and when binding is non-... 

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