OPTIMIZATION OF MOLECULAR ELECTRONIC-STRUCTURE CALCULATIONS .1. LOCAL SYMMETRY AND LOCAL SYMMETRICIZED ORBITALS

A formalism is suggested of the so‐called local symmetricized orbitals to be used for the construction of a symmetricized basis in molecular electronic structure calculations. The local symmetricized orbitals are defined as additive contributions to the symmetry orbitals of a molecule that arise from symmetry operations of a corresponding atom. The local symmetricized orbitals are transformed according to the irreducible representations of the molecular symmetry group. This approach appears to be most suitable for the optimization of quantum mechanical calculations accounting for the spatial symmetry of compounds under consideration. This fact is due to the formalism of the local symmetricized orbitals that explicitly accounts for the local symmetry of basis function centers, which is essential for such optimization. Copyright © 1990 John Wiley & Sons, Inc.