Tight Binding - Historical Background

Historical Background

By 1928, the idea of a molecular orbital had been advanced by Robert Mulliken, who was influenced considerably by the work of Friedrich Hund. The LCAO method for approximating molecular orbitals was introduced in 1928 by B. N. Finklestein and G. E. Horowitz, while the LCAO method for solids was developed by Felix Bloch, as part of his doctoral dissertation in 1928, concurrently with and independent of the LCAO-MO approach. A much simpler interpolation scheme for approximating the electronic band structure, especially for the d-bands of transition metals, is the parameterized tight-binding method conceived in 1954 by John Clarke Slater and George Fred Koster, sometimes referred to as the SK tight-binding method. With the SK tight-binding method, electronic band structure calculations on a solid need not be carried out with full rigor as in the original Bloch's theorem but, rather, first-principles calculations are carried out only at high-symmetry points and the band structure is interpolated over the remainder of the Brillouin zone between these points.

In this approach, interactions between different atomic sites are considered as perturbations. There exist several kinds of interactions we must consider. The crystal Hamiltonian is only approximately a sum of atomic Hamiltonians located at different sites and atomic wave functions overlap adjacent atomic sites in the crystal, and so are not accurate representations of the exact wave function. There are further explanations in the next section with some mathematical expressions.

Recently, in the research about strongly correlated material, the tight binding approach is basic approximation because highly localized electrons like 3-d transition metal electrons sometimes display strongly correlated behaviors. In this case, the role of electron-electron interaction must be considered using the many-body physics description.

The tight-binding model is typically used for calculations of electronic band structure and band gaps in the static regime. However, in combination with other methods such as the random phase approximation (RPA) model, the dynamic response of systems may also be studied.