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Structural and thermodynamic aspects of Li n @C x endohedral metallofullerenes: a DFT approach

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Abstract

We have determined the electronic, thermodynamic and geometrical properties of Li n @C x fullerenes by employing DFT study, which are better known as endohedral metallofullerenes (EMFs). In this work, we have considered C20, C32, C42 and C60 fullerenes and predicted the maximum number of Li atoms that can be encapsulated in their respective cavities. The identification of the geometrical structures of Li n clusters formed inside the fullerene cavity has been also included in our study. The binding energies as well as the thermodynamic properties (enthalpy, entropy and Gibbs free energy) of each EMF have been determined to acquire an idea about the stability of the EMFs. Further to ensure the stability of the EMFs, we have also calculated the deformation energy of the EMFs with respect to normal C60. By analyzing the results obtained from our calculation, we have shown that our results are in reasonably good agreement with the earlier available theoretical results. We have also performed the NPA analysis to calculate the charges on both the fullerene surface and the encapsulated Li n clusters for each Li n @C x and further investigated its variation with respect to n and x. Energy transfer phenomena from \({\text{MO}}_{{{\text{C}} - {\text{C}}}} \to {\text{LP}}_{\text{Li}}^{*}\) have been observed by employing second-order perturbation analysis. Overall, the work has provided a comprehensive idea about the characteristics and stability of all the Li n @C x -type EMFs which can be set as a benchmark for further work on the EMFs.

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Acknowledgments

TD, TB and TA are grateful to the Council of Scientific and Industrial Research (CSIR), Government of India, for providing them research fellowships. AKD gratefully acknowledges a research Grant under Scheme Number: SB/S1/PC-79/2012 from the Department of Science and Technology (DST), Govt. of India.

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Authors and Affiliations

  1. Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, 700032, India

    Tanay Debnath, Tahamida Banu, Tamalika Ash & Abhijit K. Das

  2. Department of Physics, Aliah University, Newtown, Kolkata, 700156, India

    Jayanta K. Saha

Authors
  1. Tanay Debnath
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  2. Jayanta K. Saha
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  3. Tahamida Banu
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  4. Tamalika Ash
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  5. Abhijit K. Das
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Correspondence to Abhijit K. Das.

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Debnath, T., Saha, J.K., Banu, T. et al. Structural and thermodynamic aspects of Li n @C x endohedral metallofullerenes: a DFT approach. Theor Chem Acc 135, 167 (2016). https://doi.org/10.1007/s00214-016-1919-4

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