Theoretical studies of the first- and second-row transition-metal mono- and dicarbonyl positive ions

Abstract

A b initio calculations have been carried out on the first- and second-row transition-metal mono- and dicarbonyl positive ions. The bonding in these systems is discussed in detail. Trends in the series of mono- and dicarbonyl ions and between the first- and second-row transition metals are explained in terms of a dominantly electrostatic bonding interaction and differences in metal ion state separations, ionization potentials, and s and d orbital sizes. Dissociation energies are presented and a detailed comparison is made with experimental data. Where reliable experimental data exists, agreement with the theoretical results is generally good. An exception is Mo(CO)+1,2, where the computed binding energies are much smaller than the experimental values.