Coupled Cluster and Density Functional Studies of Atomic Fluorine Chemisorption on Coronene as Model Systems for Graphene Fluorination

Hutama, Aulia S.; Hijikata, Yuh; Irle, Stephan

doi:10.1021/acs.jpcc.7b03627

Title: Coupled Cluster and Density Functional Studies of Atomic Fluorine Chemisorption on Coronene as Model Systems for Graphene Fluorination

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Abstract

Potential energy curves (PECs) of atomic fluorine adsorption on coronene as a model for graphene or nanocarbon surfaces have been computed. The PECs were obtained by scanning the fluorine atom distance to one of the center carbon atoms of the coronene molecule as model system in a “top” position from 4.0 to1.0 Å in intervals of 0.1 Å using a variety of quantum chemical methods. Various density functional theory (DFT) functionals, such as B3LYP, PBE, PBE0, CAM-B3LYP, and LC-ωPBE; approximate DFT methods such as several levels of the density-functional tight-binding (DFTB) method, as well as ab initio wave function theory methods such as MP2, CCSD, CCSD(T), and G2MS extrapolations, were used to evaluate energies for B3LYP/cc-pVDZ PEC geometries. G2MS is an approximation to the highly accurate CCSD(T)/cc-pVTZ level of theory in our work. We found that fluorine is chemically adsorbed on coronene with a binding energy of 22.9 and 23.3 kcal/mol at the B3LYP/cc-pVDZ and G2MS levels of theory, respectively, and 18.3 and 19.3 kcal/mol after counterpoise correction. Here, we found that pure DFT functionals and their DFTB approximations fail to predict the correct dissociation limit due to the DFT-inherent self-interaction error and various limitations in the DFTB approximation itself.

Authors:

Hutama, Aulia S. ^[1];

^[1];

^[2]

Nagoya University (Japan)
Nagoya University (Japan); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Publication Date:: Mon Jun 12 00:00:00 EDT 2017

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1669758

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 121; Journal Issue: 27; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Binding energy; Adsorption; Two dimensional materials; Fluorine; Energy

Citation Formats


                    Hutama, Aulia S., Hijikata, Yuh, and Irle, Stephan. Coupled Cluster and Density Functional Studies of Atomic Fluorine Chemisorption on Coronene as Model Systems for Graphene Fluorination.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.jpcc.7b03627.

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                    Hutama, Aulia S., Hijikata, Yuh, & Irle, Stephan. Coupled Cluster and Density Functional Studies of Atomic Fluorine Chemisorption on Coronene as Model Systems for Graphene Fluorination.  United States.  https://doi.org/10.1021/acs.jpcc.7b03627

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                    Hutama, Aulia S., Hijikata, Yuh, and Irle, Stephan. Mon .  
"Coupled Cluster and Density Functional Studies of Atomic Fluorine Chemisorption on Coronene as Model Systems for Graphene Fluorination".  United States.  https://doi.org/10.1021/acs.jpcc.7b03627.  https://www.osti.gov/servlets/purl/1669758.

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@article{osti_1669758,

  title        = {Coupled Cluster and Density Functional Studies of Atomic Fluorine Chemisorption on Coronene as Model Systems for Graphene Fluorination},

  author       = {Hutama, Aulia S. and Hijikata, Yuh and Irle, Stephan},

  abstractNote = {Potential energy curves (PECs) of atomic fluorine adsorption on coronene as a model for graphene or nanocarbon surfaces have been computed. The PECs were obtained by scanning the fluorine atom distance to one of the center carbon atoms of the coronene molecule as model system in a “top” position from 4.0 to1.0 Å in intervals of 0.1 Å using a variety of quantum chemical methods. Various density functional theory (DFT) functionals, such as B3LYP, PBE, PBE0, CAM-B3LYP, and LC-ωPBE; approximate DFT methods such as several levels of the density-functional tight-binding (DFTB) method, as well as ab initio wave function theory methods such as MP2, CCSD, CCSD(T), and G2MS extrapolations, were used to evaluate energies for B3LYP/cc-pVDZ PEC geometries. G2MS is an approximation to the highly accurate CCSD(T)/cc-pVTZ level of theory in our work. We found that fluorine is chemically adsorbed on coronene with a binding energy of 22.9 and 23.3 kcal/mol at the B3LYP/cc-pVDZ and G2MS levels of theory, respectively, and 18.3 and 19.3 kcal/mol after counterpoise correction. Here, we found that pure DFT functionals and their DFTB approximations fail to predict the correct dissociation limit due to the DFT-inherent self-interaction error and various limitations in the DFTB approximation itself.},

  doi          = {10.1021/acs.jpcc.7b03627},

  journal      = {Journal of Physical Chemistry. C},

  number       = 27,

  volume       = 121,

  place        = {United States},

  year         = {Mon Jun 12 00:00:00 EDT 2017},

  month        = {Mon Jun 12 00:00:00 EDT 2017}

}

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