Computed electrostatic potentials in molecules, clusters, solids and biosystems containing transition metals

Abstract

This chapter discusses computed electrostatic potentials in molecules, clusters, solids, and biosystems containing transition metals. The ability of transition metals to appear in various coordination environments, to act with ever changing- and possibly transient-oxidation states and electronic configurations have prevented the use of empirical models based on formal charges, except for the case on ionic crystals. The extension of accurate quantum chemical models to transition metal chemistry has proved more difficult than expected for entangled reasons of theory and practice. The problem of electron correlation and especially the non-dynamic correlation caused by accidental near-degeneracy of electron configurations at the atomic or molecular levels, have made problems involving transition metal atoms difficult tests of the validity and accuracy of the proposed methodological approaches. The chapter discusses the applications of molecular electrostatic potentials (MEP) to metallic and organometallic chemistry with particular emphasis on the results obtained from ab initio quantum chemical calculations.