Ab initio studies of the electronic structure and density of states of metallic beryllium

Hartree–Fock–Roothaan studies are reported for low‐lying electronic states of metallic beryllium as modeled by a moiety of 135 beryllium atoms. The system corresponds to 16 coordination shells of a central Be with internuclear separations derived from the lattice constants of the bulk metal. The calculations become tractable by use of the full D3h symmetry of the system at both the integrals and self‐consistent‐field stages and by employing ab initio effective potentials for the 1s electrons of each beryllium atom. Ionization potentials, binding energies, orbital energies, electric field gradients, nuclear‐electrostatic potentials, diamagnetic shielding constants, second moments, and Mulliken populations are calculated for selected electronic states. The calculated ionization potential for the lowest state agrees to within 10% of the experimental bulk work function. A density‐of‐states analysis for that state is reported and compared with band structure calculations.