Calculations, band theory localized electron

The delocalized (right-hand) side of Fig. 1.1 involves some form of calculation on the full lattice such as a band-theory calculation. Again, the Hartree-Fock wave function may be employed in an ab initio method or some approximate method such as Huckel band theory, or the local-exchange approximations employed leading to augmented-plane-wave or ab initio pseudopotential (PP) methods. As an alternative to band theory, the development of the ionic approach using pair potentials or modified electron-gas (MEG) theory has proved effective for certain crystalline species. 

Advances in the calculation of crystal properties by band calculations have paralleled the development of localized electron computations. Band theory... 

KNiFs has been subject to both extensive molecular orbital and to thorough band theory calculations. Newmancrystal field splitting may be derived from the calculations of Mattheiss and the value found is about 20% below the experimental figure—a situation indeed comparable to the localized electron calculations< 5) jt jg interesting that the LCAO interpretation of the band theory calculations for the monoxides< i > indicates that oxygen 2s-2p interaction with the metal and Ap orbitals may cause a greater charge redistribution than the interaction with the M orbitals. 

Finally, algorithms have been developed which incorporate electron correlation effects explicitly in wave function based band theory for crystalline solids [16, 17]. These algorithms construct the many-electron Hamiltonian matrix for a periodic system by extracting the matrix elements from calculations on finite embedded clusters. In this way the incorporation of correlation effects leads to many-electron energy bands, not only associated with hole states and added-electron states but also with excited states. More recently, Pisani and co-workers [18] introduced a post-Hartree-Fock program based on periodic local second order Mpller-Plesset perturbation theory. 

As for an appropriate band theory for the localized 4f-electron system, an attractive approach based on the p-f mixing model was proposed, and was plied to CeSb. A future problem is to refine the approach so as to carry out quantitative calculations in a self-consistent way. The anomalously large enhancement factors for the cyclotron effective masses and the y values observed in the Ce compounds cannot be explained by band structure alone. Quantitative analysis of the mass enhancement factor is a problem challenging to many-body theory. There is still much room for improvement for a complete understanding of the electronic structures of lanthanide compoimds. 

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