Structures, stabilities and spectra of endohedral mono-metallofullerenes M@C66 (M＝Ca, Sr, Ba): A first-principles study

Cui Peng; Zhang Zhuxia; Sharman Edward; Jiang Jun

doi:10.3969/j.issn.0253-2778.2020.11.006

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Open Access JUSTC Research Article

Structures, stabilities and spectra of endohedral mono-metallofullerenes M@C66 (M＝Ca, Sr, Ba): A first-principles study

1.
School of Information, Guizhou University of Finance and Economics, Guiyang 550025, China
2.
Department of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China
3.
College of Aeronautics and Astronautics, Taiyuan University of Technology, Taiyuan 030024, China
4.
Department of Neurology, University of California, Irvine, California 92697, USA

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https://doi.org/10.3969/j.issn.0253-2778.2020.11.006

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Author Bio:
Cui Peng received his Ph.D. degree in Theoretical and Computational Chemistry from Shandong University, China. He is currently an associate professor at Guizhou University of Finance and Economics. His research interests cover fullerene-based electronic devices, and high-performance computations, and machine learning.
Corresponding author: Jiang Jun (corresponding author) received his Ph.D. degree in Theoretical Chemistry at Royal Institute of Technology, Sweden. He is currently a professor at University of Science and Technology of China. His major research interests focus on the development and employment of multi-scale modeling methods for exciton kinetics in complex system, while targeting on a wide range of physics and chemistry applications such as photocatalysis, photochemistry, and nonlinear spectroscopy. E-mail: jiangj1@ustc.edu.cn
Received Date: 08 November 2020
Rev Recd Date: 25 November 2020
Publish Date: 30 November 2020

Abstract Full text PDF

Abstract

Abstract

Structures of many endohedral metallofullerenes (EMF) are still unknown because of their very low production yield, especially for endohedral mono-metallofullerenes below C70. In the present work, we investigated the alkaline earth metal encapsulated mono-metallofullerenes M@C66 (M＝Ca, Sr, Ba) theoretically, compounds which have been detected only in mass spectra. The first-principles calculations and statistical thermodynamic analysis indicate that among the C66 isomers considered, the cage C2v(4348)-C66 should be the most likely structure for M@C66, M＝Ca, Sr, Ba. These compounds may adopt another cage structure, C2(4466)-C66, at high temperatures. Both M@C2v(4384)-C66 and M@C2(4466)-C66 possess relatively large HOMO-LUMO gaps, and the former also possesses high local aromaticity. Thus it is predicted that M@C2v(4348)-C66—especially Ca@C2v(4348)-C66—could be isolable in future experiments. Moreover, simulated Vis-NIR, IR, Raman and 3C NMR spectra are provided for assisting future experimental characterizations.

Abstract

Structures of many endohedral metallofullerenes (EMF) are still unknown because of their very low production yield, especially for endohedral mono-metallofullerenes below C70. In the present work, we investigated the alkaline earth metal encapsulated mono-metallofullerenes M@C66 (M＝Ca, Sr, Ba) theoretically, compounds which have been detected only in mass spectra. The first-principles calculations and statistical thermodynamic analysis indicate that among the C66 isomers considered, the cage C2v(4348)-C66 should be the most likely structure for M@C66, M＝Ca, Sr, Ba. These compounds may adopt another cage structure, C2(4466)-C66, at high temperatures. Both M@C2v(4384)-C66 and M@C2(4466)-C66 possess relatively large HOMO-LUMO gaps, and the former also possesses high local aromaticity. Thus it is predicted that M@C2v(4348)-C66—especially Ca@C2v(4348)-C66—could be isolable in future experiments. Moreover, simulated Vis-NIR, IR, Raman and 3C NMR spectra are provided for assisting future experimental characterizations.