Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study

Niklas, Jens; Mardis, Kristy L.; Poluektov, Oleg G.

doi:10.1021/acs.jpclett.8b01613

Title: Spin Signature of the C₆₀ Fullerene Anion: A Combined X- and D-Band EPR and DFT Study

Journal Article · 03 July 2018 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.8b01613 · OSTI ID:1476900

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Argonne National Lab. (ANL), Lemont, IL (United States)
Chicago State Univ., Chicago, IL (United States)

Fullerenes attract much attention in various scientific fields, but their electronic properties are still not completely understood. Here we report on a combined EPR and DFT study of the fullerene anion C₆₀^– in solid glassy environment. DFT calculations were used to characterize its electronic structure through spin density distribution and magnetic resonance parameters. The electron spin density is not uniformly distributed throughout the C₆₀^– cage but shows a pattern similar to PC₆₁BM^–. EPR spectroscopy reveals a rhombic g-tensor sensitive to the environment in the frozen glassy solutions, which can be rationalized by deformation of the fullerenes along lowfrequency vibrational modes upon cooling. DFT modeling confirms that these deformations lead to variation in the C₆₀^– g values. Furthermore, the decrease in g-tensor anisotropy with sample annealing is related to the lessening of g-tensor strain upon temperature relaxation of the most distorted sites in the glassy state.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1476900

Journal Information:: Journal of Physical Chemistry Letters, Vol. 9, Issue 14; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C60
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EPR
Electron Paramagnetic Resonance
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PC61BM
Radical Anion
g-tensor

Title: Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study

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Title: Spin Signature of the C₆₀ Fullerene Anion: A Combined X- and D-Band EPR and DFT Study