Assessing the Predictive Power of Density Functional Theory in Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics

Ihm, Yungok S.; Park, Changwon; Jakowski, Jacek; Morris, James R.; Shim, Ji Hoon; Yong-Hyun, Kim; Sumpter, Bobby G.; Yoon, Mina

doi:10.1021/acs.jpcc.8b00793

Title: Assessing the Predictive Power of Density Functional Theory in Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics

Abstract

Density functional theory (DFT) has been widely employed to study the gas adsorption properties of surface-based or nanoscale structures. However, recent indications raise questions about the trustworthiness of some literature values, especially in terms of the DFT exchange–correlation (XC) functional. Using hydrogen adsorption on metalloporphyrin-incorporated graphenes (MPIGs) as an example, we diagnosed the trustworthiness of DFT results, meaning the range of expected variations in the DFT prediction of experimentally measurable quantities, in characterizing the gas adsorption/desorption thermodynamics. DFT results were compared in terms of XC functionals and vibrational effects that have been overlooked in the community. We decomposed free energy associated with gas adsorption into constituting components (binding energy, zero-point energy, and vibrational free energy) to systematically analyze the origin of deviations associated with the most commonly adopted DFT functionals in the field. We then quantify the deviations in the measurable quantities, such as operating temperature or pressure for hydrogen adsorption/desorption depending on the level of approximations. In conclusion, using chemical potential change associated with gas adsorption as a descriptor, we identify the required calculational accuracy of DFT to predict the room-temperature hydrogen storage material.

Authors:

Ihm, Yungok S. ^[1];

^[2];

^[3];

^[4]; Shim, Ji Hoon ^[5]; Yong-Hyun, Kim ^[6];

^[3];

^[2]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pohang Univ. of Science and Technology, Pohang (Korea)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Pohang Univ. of Science and Technology, Pohang (Korea)
Korea Advanced Institute of Science and Technology (KAIST), Daejeon (Korea)

Publication Date:: Tue Oct 09 00:00:00 EDT 2018

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

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

OSTI Identifier:: 1481709

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 45; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Ihm, Yungok S., Park, Changwon, Jakowski, Jacek, Morris, James R., Shim, Ji Hoon, Yong-Hyun, Kim, Sumpter, Bobby G., and Yoon, Mina. Assessing the Predictive Power of Density Functional Theory in Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.8b00793.

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                    Ihm, Yungok S., Park, Changwon, Jakowski, Jacek, Morris, James R., Shim, Ji Hoon, Yong-Hyun, Kim, Sumpter, Bobby G., & Yoon, Mina. Assessing the Predictive Power of Density Functional Theory in Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics.  United States.  https://doi.org/10.1021/acs.jpcc.8b00793

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                    Ihm, Yungok S., Park, Changwon, Jakowski, Jacek, Morris, James R., Shim, Ji Hoon, Yong-Hyun, Kim, Sumpter, Bobby G., and Yoon, Mina. Tue .  
"Assessing the Predictive Power of Density Functional Theory in Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics".  United States.  https://doi.org/10.1021/acs.jpcc.8b00793.  https://www.osti.gov/servlets/purl/1481709.

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@article{osti_1481709,

  title        = {Assessing the Predictive Power of Density Functional Theory in Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics},

  author       = {Ihm, Yungok S. and Park, Changwon and Jakowski, Jacek and Morris, James R. and Shim, Ji Hoon and Yong-Hyun, Kim and Sumpter, Bobby G. and Yoon, Mina},

  abstractNote = {Density functional theory (DFT) has been widely employed to study the gas adsorption properties of surface-based or nanoscale structures. However, recent indications raise questions about the trustworthiness of some literature values, especially in terms of the DFT exchange–correlation (XC) functional. Using hydrogen adsorption on metalloporphyrin-incorporated graphenes (MPIGs) as an example, we diagnosed the trustworthiness of DFT results, meaning the range of expected variations in the DFT prediction of experimentally measurable quantities, in characterizing the gas adsorption/desorption thermodynamics. DFT results were compared in terms of XC functionals and vibrational effects that have been overlooked in the community. We decomposed free energy associated with gas adsorption into constituting components (binding energy, zero-point energy, and vibrational free energy) to systematically analyze the origin of deviations associated with the most commonly adopted DFT functionals in the field. We then quantify the deviations in the measurable quantities, such as operating temperature or pressure for hydrogen adsorption/desorption depending on the level of approximations. In conclusion, using chemical potential change associated with gas adsorption as a descriptor, we identify the required calculational accuracy of DFT to predict the room-temperature hydrogen storage material.},

  doi          = {10.1021/acs.jpcc.8b00793},

  journal      = {Journal of Physical Chemistry. C},

  number       = 45,

  volume       = 122,

  place        = {United States},

  year         = {Tue Oct 09 00:00:00 EDT 2018},

  month        = {Tue Oct 09 00:00:00 EDT 2018}

}

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https://doi.org/10.1021/acs.jpcc.8b00793

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Cited by: 5 works

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Figures / Tables:

Table 1: DFT-calculated H-H bond length (d_HH in Å), metal-H₂ separation (d_MH in Å), and metal-graphene separation (d_MC in Å) for H₂-adsorbed metallo-porphyrin incorporated graphenes.

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