Linear methods in band theory

Abstract

Two approximate methods for solving the band-structure problem in an efficient and physically transparent way are presented and discussed in detail. The variational principle for the one-electron Hamiltonian is used in both schemes, and the trial functions are linear combinations of energy-independent augmented plane waves (APW) and muffin-tin orbitals (MTO), respectively. The secular equations are therefore eigenvalue equations, linear in energy. The trial functions are defined with respect to a muffin-tin (MT) potential and the energy bands depend on the potential in the spheres through potential parameters which describe the energy dependence of the logarithmic derivatives. Inside the spheres, the energy-independent APW is that linear combination of an exact solution, at the arbitrary but fixed energy ${E}_{\ensuremath{\nu}}$, and its energy derivative which matches continuously and differentiably onto the plane-wave part in the interstitial region. The energies obtained with the linear-APW method for the MT potential have errors of order ${(E\ensuremath{-}{E}_{v})}^{4}$. Similarly, the energy-independent MTO is that linear combination which matches onto that solution of the Laplace equation in the interstitial region which is regular at infinity. The energies obtained with the linear-MTO method have additional errors of order ${(E\ensuremath{-}{V}_{\mathrm{mtz}})}^{2}$, arising from the interstitial region where the potential is ${V}_{\mathrm{mtz}}$. The linear-APW (LAPW) method combines desirable features of the APW and OPW methods; it can treat $d$ bands, the energy dependence of its pseudopotential is linear and, owing to the smoothness of the energy-independent APW at the spheres, non-MT contributions to the potential are included principally through their Fourier components. The linear-MTO (LMTO) method is particularly suited for closely packed structures and it combines desirable features of Korringa-Kohn-Rostoker, linear-combination-of-atomic-orbitals, and cellular methods; the secular matrix is linear in energy, the overlap integrals factorize as potential parameters and structure constants, the latter are canonical in the sense that they neither depend on the energy nor the cell volume and they specify the boundary conditions on a single MT or atomic sphere in the most convenient way. This method is very well suited for self-consistent calculations. The empty-lattice test is applied to the linear-MTO method and the free-electron energy bands are accurately reproduced. Finally, it is shown how relativistic effects may be included in both the LAPW and LMTO methods.