Ab initio characterization of graphene nanoribbons and their polymer precursors

Bottom-up fabrication of graphene nanoribbons (GNRs) from halogen-terminated aromatic precursors is a promising method for achieving atomically precise nanoribbons at competitive yields. GNR fabrication proceeds via the polymerization of the precursors and successive dehydrogenation. By first principles density functional theory calculations, we perform a systematic characterization of the polymeric precursors and the corresponding graphene nanoribbons in terms of structural and electronic properties, and we compute the Raman and infrared spectra. The band structure properties are examined by considering the bonding features and the partial charge densities of the structures. The physical origin of the infrared and Raman peaks is investigated in terms of the morphology and vibrational properties of the precursors and products. We show that light spectroscopy provides a unique fingerprint for each type of GNR, which may be used to monitor the quality of the final products and the kinetics of the synthesis process.