Correlation between atomistic morphology and electron transport properties in defect-free and defected graphene nanoribbons: An interpretation through Clar sextet theory

Structural, electronic and transport properties of defect-free, defected and functionalized armchair and zig-zag graphene nanoribbons (GNRs) are investigated with density functional theory and non-equilibrium Green’s function calculations and rationalized in terms of Clar’s theory of the aromatic sextet. Calculations suggest a tight relationship between the transport properties of nanoribbons and the underlying bond patterning as described by valence bond and Clar sextet theory. Namely, armchair GNRs exhibit a strong dependence of the transport properties on the ribbon width, as a consequence of different valence bond representations. The occurrence of localized defects involving electron pairs does not significantly alter this behavior. Conversely, transport properties of zigzag GNRs are less affected by morphological details, such as width and occurrence of defects, as expected from the application of Clar’s theory. However, controlled edge functionalization and morphology modifications in zigzag GNRs can potentially lead to localization of aromatic sextets and, consequently, to strong changes in the transport properties. Our work indicates Clar sextet theory as a powerful and accurate tool to rationalize and predict the electronic and transport properties of complex carbon nanostructures based on GNRs. These principles can be extended to the design of novel systems with potential applications in nanoelectronics.