A Crystal Orbital approach for two‐ and three‐dimensional solids on the basis of CNDO/INDO Hamiltonians. Basis equations

Abstract

AbstractA Hartree–Fock (HF) self‐consistent field (SCF) crystal orbital (CO) formalism for two‐ and three‐dimensional (2D/3D) solids on the basis of semiempirical CNDO/INDO (complete neglect of differential overlap; intermediate neglect of differential overlap) Hamiltonians is presented. The employed SCF variants allow for the treatment of atomic species up to bromine under the inclusion of the first (i.e., 3d) transition metal series. Band structure investigations of 2D and 3D materials containing more than 30 atoms per unit cell are feasible by the present SCF HF CO formalism. The theoretical background of the computational scheme is given in this contribution. Special emphasis is placed on physically reliable truncation criteria for the lattice sums, the adaptation of the crystal symmetry in k space, as well as the suitable choice of domains in Brillouin zone (BZ) integrations required in the determination of charge‐density matrices. The capability and limitations of the semiempirical SCF HF CO approach is demonstrated for some simpler solids by comparing the present computational results with those of ab initio CO schemes as well as conventional numerical methods in soid‐state theory. The employed model solids are graphite and BN (2D and 3D networks for both solids) as well as diamond, silicon, germanium, and TiS2.