Localized orbital calculations of the bonding in SO,SO2F2, ClO3F and SOCL2

Localized valence molecular orbitals have been obtained for SO, SO₂F₂, ClO₃F and SOCl₂ by the method due to Boys and Foster. The bonding in these molecules, in which the second row atom is exhibiting an excess valency, is discussed in terms of the form of these localized orbitals. The bonding of the second row atom to an oxygen atom is described by three bent bond orbitals, whilst bonding to a halogen atom is described by a single bond orbital. The participation of 3d functions in the various bonding and nonbonding orbitals is analysed in this localized orbital framework.