Interpretation of molecular device transport calculations

Abstract

The field of molecular electronics will benefit from rational design approaches based on a complete understanding of the electronic structure of molecule-based devices. However, many computational approaches that are used to study molecular-scale devices are based on methods that have deficiencies that must be understood in order for those methods to be useful to the modeling and experimental community. Density-functional theory based methods have some well-known pitfalls that limit their application to the study of electron transport in models of molecular junction devices. Some of the impacts of these deficiencies are highlighted in this work through the use of a graphene model system and a variety of simple hydrocarbon molecules. Self-interaction error in simple functionals built from the local density approximation and the generalized gradient approximation results in very large errors in predicted absolute and relative ionization potentials. This demonstrates that electron transmission spectra predicted using these functionals should be considered with caution. We also demonstrate that care must be taken with the use of finite models for electrodes.