Ab initio quantum chemical study of electron transfer in carboranes

The electron transfer (ET) properties of 10- and 12-vertex carboranes are investigated by the ab initio Hartree–Fock method within the Marcus-Hush (MH) two-state model and the Koopman theorem (KT) approach. The calculated value of the ET coupling matrix element, VAB, is consistently higher in the KT approach than in the MH two-state model. For the carborane molecules functionalized by –CH2 groups at C-vertices, VAB strongly depends on the relative orientation of the planes containing the terminal –CH2 groups. The predicted conformation dependence of VAB offers a molecular mechanism to control ET between two active centers in molecular systems.