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Modeling zigzag CNT: dependence of structural and electronic properties on length, and application to encapsulation of HCN and C2H2

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Abstract

Density functional theory (B3LYP, B3LYP-D2 and wB97XD functionals) was used in finite models of zigzag carbon nanotubes (CNT), (n,0)×k with n = 6–9 and k = 2–4, to systematically investigate the effects of size on their structural and electronic properties. We found that the ratio between the length (L t) and the diameter (d t) of the pristine CNT has to be larger than 2, i.e., L t/d t > 2, in order to provide the observed experimental trends of C=C bond distances, as well as to maintain the atomic charges nearly constant and zero around the center of the tube. Therefore, the concepts of useful length and volume were developed and tested for the encapsulation process of HCN and C2H2 into CNTs. The energies involved in these processes, as well as the changes in molecular structure and electronic properties of the dopants and the CNTs are discussed and rationalized by the amount of charge transferred between dopant and CNT.

Illustration of zigzag CNT length and diameter ratio in order to represent C=C bond experimental trend

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Acknowledgments

The authors are thankful to the Brazilian funding agencies Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Fundação de Amparo à Ciência e Tecnologia do Estado de Pernambuco (FACEPE) and Instituto Nacional de Ciência e Tecnologia: Nanotecnologia para Marcadores Integrados (inct-INAMI) for supporting the Computational and Theoretical Chemistry Laboratory of Departamento de Química Fundamental-Universidade Federal de Pernambuco (dQF-UFPE) and the Centro Nacional de Processamento de Alto Desempenho de Pernambuco (CENAPAD-PE) where this work was developed. Some calculations were performed on the High Performance Computing Center (HPCC) at the University of Florida, which is gratefully acknowledged. E.C. de Aguiar thanks CAPES and FACEPE for the scholarships, and R.L.L. thanks CNPq for the PQ-fellowship (Proc. no. 308823/2014-1).

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Authors and Affiliations

  1. Unidade Acadêmica de Serra Talhada, Universidade Federal Rural de Pernambuco (UFRPE), 56909-535, Serra Talhada, PE, Brazil

    Eduardo C. Aguiar

  2. Departamento de Química Fundamental, Universidade Federal de Pernambuco (UFPE), 50740-540, Recife, PE, Brazil

    Ricardo L. Longo & João Bosco P. da Silva

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  1. Eduardo C. Aguiar
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  2. Ricardo L. Longo
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  3. João Bosco P. da Silva
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Correspondence to Eduardo C. Aguiar.

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This paper belongs to Topical Collection Brazilian Symposium of Theoretical Chemistry (SBQT 2015)

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Aguiar, E.C., Longo, R.L. & da Silva, J.B.P. Modeling zigzag CNT: dependence of structural and electronic properties on length, and application to encapsulation of HCN and C2H2 . J Mol Model 23, 144 (2017). https://doi.org/10.1007/s00894-017-3319-7

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