Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study

Mardis, Kristy L.; Webb, J.; Holloway, Tarita; Niklas, Jens; Poluektov, Oleg G.

doi:10.1021/acs.jpclett.5b02111

Title: Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study

Abstract

Organic photovoltaic (OPV) devices are a promising alternative energy source. Attempts to improve their performance have focused on the optimization of electron-donating polymers, while electron-accepting fullerenes have received less attention. Here, we report an electronic structure study of the widely used soluble fullerene derivatives PC61BM and PC71BM in their singly reduced state, that are generated in the polymer:fullerene blends upon light-induced charge separation. Density functional theory (DFT) calculations characterize the electronic structures of the fullerene radical anions through spin density distributions and magnetic resonance parameters. The good agreement of the calculated magnetic resonance parameters with those determined experimentally by advanced electron paramagnetic resonance (EPR) allows the validation of the DFT calculations. Thus, for the first time, the complete set of magnetic resonance parameters including directions of the principal g-tensor axes were determined. For both molecules, no spin density is present on the PCBM side chain, and the axis of the largest g-value lies along the PCBM molecular axis. While the spin density distribution is largely uniform for PC61BM, it is not evenly distributed for PC71BM.

Authors:

Mardis, Kristy L. ^[1]; Webb, J. ^[1]; Holloway, Tarita ^[1]; Niklas, Jens ^[2]; Poluektov, Oleg G. ^[2]

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

Publication Date:: Thu Dec 03 00:00:00 EST 2015

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

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

OSTI Identifier:: 1236808

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry Letters

Additional Journal Information:: Journal Volume: 6; Journal Issue: 23; Journal ID: ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 14 SOLAR ENERGY; Electron Transfer; Polaron; Radical Anion; Spin Density; g-tensor

Citation Formats


                    Mardis, Kristy L., Webb, J., Holloway, Tarita, Niklas, Jens, and Poluektov, Oleg G. Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.jpclett.5b02111.

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                    Mardis, Kristy L., Webb, J., Holloway, Tarita, Niklas, Jens, & Poluektov, Oleg G. Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study.  United States.  https://doi.org/10.1021/acs.jpclett.5b02111

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                    Mardis, Kristy L., Webb, J., Holloway, Tarita, Niklas, Jens, and Poluektov, Oleg G. Thu .  
"Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study".  United States.  https://doi.org/10.1021/acs.jpclett.5b02111.  https://www.osti.gov/servlets/purl/1236808.

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@article{osti_1236808,

  title        = {Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study},

  author       = {Mardis, Kristy L. and Webb, J. and Holloway, Tarita and Niklas, Jens and Poluektov, Oleg G.},

  abstractNote = {Organic photovoltaic (OPV) devices are a promising alternative energy source. Attempts to improve their performance have focused on the optimization of electron-donating polymers, while electron-accepting fullerenes have received less attention. Here, we report an electronic structure study of the widely used soluble fullerene derivatives PC61BM and PC71BM in their singly reduced state, that are generated in the polymer:fullerene blends upon light-induced charge separation. Density functional theory (DFT) calculations characterize the electronic structures of the fullerene radical anions through spin density distributions and magnetic resonance parameters. The good agreement of the calculated magnetic resonance parameters with those determined experimentally by advanced electron paramagnetic resonance (EPR) allows the validation of the DFT calculations. Thus, for the first time, the complete set of magnetic resonance parameters including directions of the principal g-tensor axes were determined. For both molecules, no spin density is present on the PCBM side chain, and the axis of the largest g-value lies along the PCBM molecular axis. While the spin density distribution is largely uniform for PC61BM, it is not evenly distributed for PC71BM.},

  doi          = {10.1021/acs.jpclett.5b02111},

  journal      = {Journal of Physical Chemistry Letters},

  number       = 23,

  volume       = 6,

  place        = {United States},

  year         = {Thu Dec 03 00:00:00 EST 2015},

  month        = {Thu Dec 03 00:00:00 EST 2015}

}

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Title: Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study

Abstract

Citation Formats

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Efficient and accurate approximations to the molecular spin-orbit coupling operator and their use in molecular g-tensor calculations journal, January 2005

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Self-Trapped Excitons in Ionic-Covalent Silver Halide Crystals and Nanostructures: High-Frequency EPR, ESE, ENDOR and ODMR Studies
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Spectroscopic Signatures of Photogenerated Radical Anions in Polymer-[C ₇₀ ]Fullerene Bulk Heterojunctions
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Photoinduced Dynamics of Charge Separation: From Photosynthesis to Polymer–Fullerene Bulk Heterojunctions
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Electronic Structure of the P₇₀₀ Special Pair from High-Frequency Electron Paramagnetic Resonance Spectroscopy
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Density‐functional thermochemistry. III. The role of exact exchange
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Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

Quantum chemistry in parallel with PQS
journal, January 2009

The ORCA program system: The ORCA program system
journal, June 2011

Development and validation of reliable quantum mechanical approaches for the study of free radicals in solution
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Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
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Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992

Efficient and accurate approximations to the molecular spin-orbit coupling operator and their use in molecular g-tensor calculations
journal, January 2005

New insights into polymer solar cells stability: The crucial role of PCBM oxidation
journal, July 2018

Charge Transfer State in the Composite DTS(FBTTh2)2:PC71BM: Dynamics of Electron–Hole Distance Distribution After Light Absorption
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Synthesis and Photophysical Study of [60]Fullerene-Maleimide Dyads
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