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

Abstract

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.

Authors:

^[1];

^[2];

^[1]

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

Publication Date:: 2018-07-03

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

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

OSTI Identifier:: 1476900

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry Letters

Additional Journal Information:: Journal Volume: 9; Journal Issue: 14; Journal ID: ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; C60; DFT; Density Functional Theory; EPR; Electron Paramagnetic Resonance; Fullerene; PC61BM; Radical Anion; g-tensor

Citation Formats


                    Niklas, Jens, Mardis, Kristy L., and Poluektov, Oleg G. Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpclett.8b01613.

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                    Niklas, Jens, Mardis, Kristy L., & Poluektov, Oleg G. Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study.  United States.  https://doi.org/10.1021/acs.jpclett.8b01613

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                    Niklas, Jens, Mardis, Kristy L., and Poluektov, Oleg G. Tue .  
"Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study".  United States.  https://doi.org/10.1021/acs.jpclett.8b01613.  https://www.osti.gov/servlets/purl/1476900.

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@article{osti_1476900,

  title        = {Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study},

  author       = {Niklas, Jens and Mardis, Kristy L. and Poluektov, Oleg G.},

  abstractNote = {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.},

  doi          = {10.1021/acs.jpclett.8b01613},

  journal      = {Journal of Physical Chemistry Letters},

  number       = 14,

  volume       = 9,

  place        = {United States},

  year         = {2018},

  month        = {7}

}

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Works referencing / citing this record:

Linear and sublinear scaling computation of the electronic g-tensor at the density functional theory level
journal, January 2019

Glasbrenner, Michael; Vogler, Sigurd; Ochsenfeld, Christian
The Journal of Chemical Physics, Vol. 150, Issue 2
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Title: Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study

Abstract

Citation Formats

Carbon nanomaterials in tribology journal, August 2017

Fullerene derivative acceptors for high performance polymer solar cells journal, January 2011

Photoinduced Electron Transfer from a Conducting Polymer to Buckminsterfullerene journal, November 1992

Contribution of the relativistic mass correction to the g tensor of molecules journal, April 1989

Comparison of Electron Paramagnetic Resonance Line Shapes and Electron Spin Relaxation Rates for C 60 - and C 60 3- in 4:1 Toluene:Acetonitrile and Dimethyl Sulfoxide journal, January 1996

Electrochemical Generation and Electron Paramagnetic Resonance Studies of C60-, C602-, and C603- journal, April 1994

EPR spectra of C60 anions journal, June 1996

Buckminsterfulleride(1-) salts: synthesis, EPR, and the Jahn-Teller distortion of C60-. [Erratum to document cited in CA119:116920] journal, July 1994

Buckminsterfulleride(1-) salts: synthesis, EPR, and the Jahn-Teller distortion of C60- journal, June 1993

The universality of the electron spin relaxation in C60 mono radical anion salts: EPR studies of the model system [P(C6H5)4]2C60X journal, June 1996

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

Carbon nanomaterials in tribology
journal, August 2017

Fullerene derivative acceptors for high performance polymer solar cells
journal, January 2011

Photoinduced Electron Transfer from a Conducting Polymer to Buckminsterfullerene
journal, November 1992

Contribution of the relativistic mass correction to the g tensor of molecules
journal, April 1989

Comparison of Electron Paramagnetic Resonance Line Shapes and Electron Spin Relaxation Rates for C ₆₀ ^- and C ₆₀ ^3- in 4:1 Toluene:Acetonitrile and Dimethyl Sulfoxide
journal, January 1996

Electrochemical Generation and Electron Paramagnetic Resonance Studies of C60-, C602-, and C603-
journal, April 1994

EPR spectra of C60 anions
journal, June 1996

Buckminsterfulleride(1-) salts: synthesis, EPR, and the Jahn-Teller distortion of C60-. [Erratum to document cited in CA119:116920]
journal, July 1994

Buckminsterfulleride(1-) salts: synthesis, EPR, and the Jahn-Teller distortion of C60-
journal, June 1993

The universality of the electron spin relaxation in C60 mono radical anion salts: EPR studies of the model system [P(C6H5)4]2C60X
journal, June 1996

How many bound valence states does the C ₆₀ ⁻ anion have?
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journal, January 1996

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journal, November 1994

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journal, April 1993

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journal, August 1980

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journal, January 1988

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