PUB - Publikationen an der Universität Bielefeld

A method for non-relativistic self-consistent field (SCF) electronic structure calculations for polyatomic molecules is described, which retains the linear combination of atomic orbitals ansatz for molecular orbitals (MO-LCAO), but replaces the usual algebraic expansion of atom-centred radial parts in terms of basis functions (usually some kind of Gauss-type functions) by a numerical representation on a set of radial grid points around each centre. The radial parts are optimized, according to the variation principle, until self-consistency is achieved. Even though Fourier integral transform techniques are used the method works completely in ordinary space. Intermediate quantities defined in momentum space are evaluated in closed form.