PNNL

Abstract

Advances in understanding the kinetic behavior of certain environmental electron transfer (ET) systems are presented. Emphasis is placed on the homogeneous ET chemistry of transition metals, particularly the FeII/III system, in various relevant forms. In the context of modern ET theory, we examine the utility of computational chemistry methods for the calculation of ET quantities such as the reorganization energy and electronic coupling matrix element. We discuss successful application of the methods to topics of homogeneous oxidation of dissolved metal ions by molecular oxygen in aqueous solution, as well as the prediction of electron mobility in solid phase iron oxide crystals. The examples illustrate the significant potential for many more advances in understanding environmental ET systems through the combination of ET theory and computational chemistry.