Strictly localized orbitals from spatial partitioning with the discontinuous Galerkin method

Abstract

We present a rigorous electronic-structure theory of strictly localized orbitals associated with a spatial partition of the one-electron Hilbert space that remains well defined in the complete basis-set limit. Each strictly localized orbital is supported on a spatial domain and may be discontinuous at domain interfaces. Using the interior-penalty discontinuous Galerkin method, these strictly localized orbitals can be employed in variational electronic-structure calculations despite their discontinuities at domain interfaces. As a proof of concept, we present numerical illustrations on one-dimensional diatomic model systems. They show that variational calculations can be carried out in a basis of strictly localized orbitals while maintaining good agreement with conventional calculations. Moreover, these strictly localized orbitals naturally lead to chemically intuitive representations of many-electron wave functions in the spirit of valence-bond theory.