The electronic band structure of graphite has been calculated from an ab initio variational approach using a linear-combination of atomic-orbitals (LCAO) basis of Bloch states, including nonspherical terms in the one-electron crystal potential. Matrix elements of the Hamiltonian are evaluated directly without any tight-binding approximations. The optical transitions deduced from the energy bands calculated using a single-layer crystal model agree nicely with recent polarized-light reflectance measurements. Details of the band structure are calculated for the three-dimensional Brillouin zone and related to the results obtained using the single-layer crystal structure. The results are encouraging, not only from the standpoint that the method employed is an ab initio approach with no special a priori assumptions, but also because the band structure is quite insensitive to the particulars of the crystal potential function.

• Received 26 January 1970

DOI:https://doi.org/10.1103/PhysRevB.1.4747