Symmetry decomposition of quantum chemical bond orders

Two schemes based on atomic orbital symmetry for the decomposition of Mayer, B-AB, and Wilberg, W-AB, bond order indices into the sigma-, pi-, and delta-components (AOSB-A) or into the in-plane and out-of-plane-components (AOSB-P) are proposed. The AOSB-A approach is based on the sorting of the A and B atoms atomic orbitals according to their symmetry relative to the line of A-B bonding, the AOSB-P scheme uses AO sorting relative to the plane of molecule or fragment. The AOSB technique was applied to a wide range of species including organic molecules, inorganic molecules of main group elements, transition metal complexes and complexes with multiple metal-metal bond. (C) 2008 Elsevier B.V. All rights reserved.