Computational applications in organic electrochemistry

Two features of particular interest in organic electrochemistry are the reduction and/or oxidation potentials of organic substances and the structures of electrochemically generated intermediates. The development of accurate quantum chemical methods for determining the in recent years, together with continued improvements in computing technology with which to implement such methods, has resulted in opportunities to solve problems in chemistry that cannot be solved by experiment. Two major areas which have benefited most by the availability of computational technology are improved methods for (a) prediction of redox potentials of organic species and (b) determination of the structure of electrochemically generated ion pairs. The ability to predict the reduction or oxidation potential of an unknown substance can be of value in several ways: in planning for carrying out a reaction with a mediator of electron transfer, one can compute the redox potentials of likely compounds to choose the best candidate before setting out on what might be a lengthy synthetic program and when trying to analyze a complex reaction mechanism, one can compute the redox potentials of likely short-lived intermediates. The structures of electrogenerated intermediates can offer new insights into the binding between charged species.