Discrete variational method for the energy-band problem with general crystal potentials

A general variational method for efficiently calculating energy bands and charge densities in solids is presented; the method can be viewed as a weighted local-energy procedure or alternately as a numerical integration scheme. This rapidly convergent procedure circumvents many of the difficulties associated with the evaluation of matrix elements of the Hamiltonian in an arbitrary basis and treats the general nonspherical potential with no more complication than the usual "muffin-tin" approximation. Thus the band structure of ionic and covalent materials can be calculated with realistic crystal potentials. As an example, the method is applied to the one-electron model Hamiltonian with a nonspherical local potential, using a linear combination of atomic orbitals basis. Matrix elements of the Hamiltonian are evaluated directly without decomposition into atomic basis integrals; no "tight-binding" approximations are made. Detailed calculations are presented for the band structure and charge density of bcc lithium which demonstrate the feasibility of our method, and reveal the sensitivity of the energy bands to nonspherical and exchange components of the crystal potential. Various prescriptions for the construction of crystal potentials are considered, and convenient least-squares expansions are described. The extension of these methods to nonlocal potentials such as are encountered in the Hartree-Fock self-consistent-field procedure is discussed.