Exact‐exchange Hartree–Fock calculations for periodic systems. I. Illustration of the method

Abstract A scheme is presented for performing linear‐combination‐of‐atomic‐orbitals ( LCAO ) self‐consistent‐field ( SCF ) ab initio Hartree–Fock calculations of the electronic structure of periodic systems. The main aspects which characterize the present method are (i) a thorough discussion of both translational and local symmetry properties and the derivation of general formulas for the transformation of all the relevant monoelectronic and bielectronic terms under symmetry operators. (ii) The use of general yet powerful criteria for the truncation of infinite sums; in particular, the Coulomb electron–electron interactions are subdivided into terms corresponding to intersecting or nonintersecting charge distributions; the latter are grouped into shell contributions and the interaction is evaluated by multipolar expansions; the exchange interaction may be evaluated with great precision by retaining a relatively small number of two‐electron integrals according to a truncation criterion which fully preserves its nonlocal character. (iii) The use of a procedure for performing integrals over k , as needed in the evaluation of the Fermi energy and in the reconstruction of the Fock matrix, which is particularly simple because it employs partially intersecting small spheres as integration subdomains where linear extrapolation is admitted. A comparison is finally made of our fundamental equations in the critical SCF stage with those obtainable by a recent proposal which uses Fourier transforms to express Coulomb and exchange integrals.