Charges and bond orders in covalent xenon compounds using the structure—resonance paradigm

Abstract

An empirical structure-resonance theory model for the xenon fluorides and oxyfluorides is examined, and quantitative estimates of atom charges and bond orders are derived. The results are correlated with other theoretical estimates and with related experimental properties. Realistic representations of molecular structures for the compounds containing xenon with higher oxidation states require that large numbers of octet structures, ionic resonance forms and/or expanded valence shell structures contribute to the final resonance hybrids. The representation of the effective structure—resonance theory Hamiltonian matrix by a graph allows the resulting high dimension eigenproblem to be greatly reduced using graph theoretical topological and symmetry restraints. XeF bond orders and fluorine atom charges are found to show little variation over the entire range of xenon oxidation state. The calculated xenon charges are generally much smaller but proportional to the formally assigned oxidation numbers.