Dirac point resonances due to atoms and molecules adsorbed on graphene and transport gaps and conductance quantization in graphene nanoribbons with covalently bonded adsorbates

Abstract

We present a tight binding theory of the Dirac point resonances due to adsorbed atoms and molecules on an infinite 2D graphene sheet based on the standard tight binding model of the graphene p-band electronic structure and the extended Huckel model of the adsorbate and nearby graphene carbon atoms. The relaxed atomic geometries of the adsorbates and graphene are calculated using density functional theory. Our model includes the effects of the local rehybridization of the graphene from the sp^2 to sp^3 electronic structure that occurs when adsorbed atoms or molecules bond covalently to the graphene. Unlike in previous tight-binding models of Dirac point resonances, adsorbed species with multiple extended molecular orbitals and bonding to more than one graphene carbon atom are treated. More accurate and more general analytic expressions for the Green's function matrix elements that enter the T-matrix theory of Dirac point resonances than have been available previously are obtained. We study H, F, OH and O adsorbates on graphene and for each we find a strong scattering resonance (two resonances for O) near the Dirac point of graphene, by far the strongest and closest to the Dirac point being the resonance for H. We extract a minimal set of tight binding parameters that can be used to model resonant electron scattering and electron transport in graphene and graphene nanostructures with adsorbed H, F, OH and O accurately and efficiently. We also compare our results for the properties of Dirac point resonances due to adsorbates on graphene with those obtained by others using density functional theory-based electronic structure calculations, and discuss their relative merits. We then present calculations of electronic quantum transport in graphene nanoribbons with these adsorbed species...