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Effects of shape, size, and pyrene doping on electronic properties of graphene nanoflakes

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Abstract

Effects of size, shape, and pyrene doping on electronic properties of graphene nanoflakes (GNFs) were theoretically investigated using density functional theory method with PBE, B3PW91, and M06-2X functionals and cc-pVDZ basis set. Two shapes of zigzag GNFs, hexagonal (HGN) and rhomboidal (RGN), were considered. The energy band gap of GNF depends on shape and decreases with size. The HGN has larger band gap energy (1.23–3.96 eV) than the RGN (0.13–2.12 eV). The doping of pyrene and pyrene derivatives on both HGN and RGN was also studied. The adsorption energy of pyrene and pyrene derivatives on GNF does not depend on the shape of GNFs with energies between 21 and 27 kcal mol−1. The substituent on pyrene enhances the binding to GNF but the strength does not depend on electron withdrawing or donating capability. The doping by pyrene and pyrene derivatives also shifts the HOMO and LUMO energies of GNFs. Both positive (destabilizing) and negative (stabilizing) shifts on HOMO and LUMO of GNFs were seen. The direction and magnitude of the shift do not follow the electron withdrawing and donating capability of pyrene substituents. However, only a slight shift was observed for doped RGN. A shift of 0.19 eV was noticed for HOMO of HGN doped with 1-aminopyrene (pyNH2) and of 0.04 eV for LUMO of HGN doped with 1-pyrenecarboxylic acid (pyCOOH).

HOMO and LUMO Energies of pyrene/pyrene derivatives doped Graphene Nanoflakes

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Acknowledgments

The authors would like to acknowledge the 90th anniversary of Chulalongkorn University for Mr.Thanawit Kuamit’s scholarship and Ratchadapisek Somphot Endownment Fund of Chulalongkorn University RES560530184-AM and CU-57-038-AM (Advanced Material Cluster) and the world class university grant of the comission for higher education WCU-031-AM-57 for funding this work. Additionally, the Center of Excellence in Computational Chemistry (CECC), Department of Chemistry, Chulalonkorn University and the National Electronics and Computer Technology Center (NECTEC) under the National e-Science Consortium are gratefully acknowledged for their support in computing facilities.

This work is devoted to the remembrance of His Majesty King Bhumibol Adulyadej (1927-2016), for his life-time dedication to Thailand.

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Authors and Affiliations

  1. Center of Excellence in Computational Chemistry, Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand

    Thanawit Kuamit, Manussada Ratanasak & Vudhichai Parasuk

  2. National Nanotechnology Center National Science and Technology Development Agency, 130 Thailand Science Park, Paholyothin Rd, Klong Luang, Pathumthani, 12120, Thailand

    Chompoonut Rungnim

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  1. Thanawit Kuamit
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Kuamit, T., Ratanasak, M., Rungnim, C. et al. Effects of shape, size, and pyrene doping on electronic properties of graphene nanoflakes. J Mol Model 23, 355 (2017). https://doi.org/10.1007/s00894-017-3521-7

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