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On the radicalar properties of graphene fragments: double-hybrid DFT and perturbation theory approaches

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Abstract

The physical–chemical properties of polycyclic aromatic hydrocarbons (PAHs), molecules formed by fused carbon rings passivated by hydrogen atoms, make them attractive to several applications, including light-emitting diodes, photovoltaic cells, and transistors. They borrow some of the unique properties of graphene, nanotubes, and fullerenes. Additionally, radicals related to these structures may be involved in carcinogenic effects. In this work, electronic and energetic aspects of PAHs, including triangulenes, were analyzed using BLYP and B2PLYP density functionals as well as with unrestricted Hartree–Fock (UHF) and second-order Møller–Plesset perturbation (MP2) theories. The results show that DFT BLYP and B2PLYP functionals predict adiabatic singlet–triplet energy gap in better agreement to reference data when compared to MP2, with the double-hybrid B2PLYP producing better results than BLYP. On the other hand, for calculation of properties involving radical species, as homolytic bond dissociation energies, B2PLYP overestimates the binding energy, especially for larger PAHs. The erratic behavior of UHF and MP2 for open-shell species limits the B2PLYP performance regarding the stability analysis of triangulenes over different multiplicities.

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Acknowledgements

The authors thank the Brazilian agencies Fundação de Apoio à Pesquisa do Estado de São Paulo—FAPESP (17/23416-9), Conselho Nacional de Desenvolvimento Científico e Tecnológico—CNPq (306177/2016-1, 423022/2018-0 and 306585/2019-7) for financial support. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)—Finance Code 001.

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  1. Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, Santo André, SP, 09210-580, Brazil

    Michele A. Salvador, Felipe C. T. Antonio, Gabriela D. da Silva, Fernando H. Bartoloni, Mauricio D. Coutinho-Neto & Paula Homem-de-Mello

  2. Escola de Engenharia Industrial Metalúrgica, Universidade Federal Fluminense, Av. dos Trabalhadores, 420, Volta Redonda, RJ, 27255-125, Brazil

    Ednilsom Orestes

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  1. Michele A. Salvador
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Salvador, M.A., Antonio, F.C.T., da Silva, G.D. et al. On the radicalar properties of graphene fragments: double-hybrid DFT and perturbation theory approaches. Theor Chem Acc 139, 118 (2020). https://doi.org/10.1007/s00214-020-02632-w

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