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Performance of Dispersion-Inclusive Density Functional Theory Methods for Energetic Materials

  • Dana O’Connor
    Dana O’Connor
    Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
  • Imanuel Bier
    Imanuel Bier
    Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
    More by Imanuel Bier
  • Yun-Ting Hsieh
    Yun-Ting Hsieh
    Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
  • , and 
  • Noa Marom*
    Noa Marom
    Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
    Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
    Department of Physics, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
    *Email: [email protected]
    More by Noa Marom
Cite this: J. Chem. Theory Comput. 2022, 18, 7, 4456–4471
Publication Date (Web):June 27, 2022
https://doi.org/10.1021/acs.jctc.2c00350
Copyright © 2022 American Chemical Society

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    Abstract

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    Molecular crystals of energetic materials (EMs) are denser than typical molecular crystals and are characterized by distinct intermolecular interactions between nitrogen-containing moieties. To assess the performance of dispersion-inclusive density functional theory (DFT) methods, we have compiled a data set of experimental sublimation enthalpies of 31 energetic materials. We evaluate the performance of three methods: the semilocal Perdew–Burke–Ernzerhof (PBE) functional coupled with the pairwise Tkatchenko-Scheffler (TS) dispersion correction, PBE with the many-body dispersion (MBD) method, and the PBE-based hybrid functional (PBE0) with MBD. Zero-point energy contributions and thermal effects are described using the quasi-harmonic approximation (QHA), including explicit treatment of thermal expansion, which we find to be non-negligible for EMs. The lattice energies obtained with PBE0+MBD are the closest to experimental sublimation enthalpies with a mean absolute error of 9.89 kJ/mol. However, the state-of-the-art treatment of vibrational and thermal contributions makes the agreement with experiment worse. Pressure–volume curves are also examined for six representative materials. For pressure–volume curves, all three methods provide reasonable agreement with experimental data with mean absolute relative errors of 3% or less. Most of the intermolecular interactions typical of EMs, namely nitro-amine, nitro–nitro, and nitro-hydrogen interactions, are more sensitive to the choice of the dispersion method than to the choice of the exchange-correlation functional. The exception is π–π stacking interactions, which are also very sensitive to the choice of the functional. Overall, we find that PBE+TS, PBE+MBD, and PBE0+MBD do not perform as well for energetic materials as previously reported for other classes of molecular crystals. This highlights the importance of testing dispersion-inclusive DFT methods for diverse classes of materials and the need for further method development.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jctc.2c00350.

    • Tabulated chemical names and experimental sublimation enthalpies of benchmark systems; verification of PBE0+MBD single point lattice energies; comparison of ZPE obtained within harmonic approximation with lower level vs higher level settings; additional details of QHA calculations of constant pressure heat capacity; vacuum space convergence plots for interaction energy analysis; tabulated values of computed lattice energies and thermal correction terms; tabulated values of thermal expansion; and tabulated values of interaction energies (PDF)

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    Cited By

    This article is cited by 4 publications.

    1. Mi Yan, Liyuan Wei, Yiyi Xiao, Weiping Xian, Zihan Wang, Shichun Li, Jinjiang Xu, Yu Liu, Fude Nie, Shiliang Huang. Thermal Expansion, Atomic Vibration, and Molecular Conformation of β-HMX at a Wide Temperature Range Prior to Phase Transformation. The Journal of Physical Chemistry C 2023, 127 (42) , 20838-20848. https://doi.org/10.1021/acs.jpcc.3c03551
    2. Dana O’Connor, Imanuel Bier, Rithwik Tom, Anna M. Hiszpanski, Brad A. Steele, Noa Marom. Ab Initio Crystal Structure Prediction of the Energetic Materials LLM-105, RDX, and HMX. Crystal Growth & Design 2023, 23 (9) , 6275-6289. https://doi.org/10.1021/acs.cgd.3c00027
    3. Rithwik Tom, Siyu Gao, Yi Yang, Kaiji Zhao, Imanuel Bier, Eric A. Buchanan, Alexandr Zaykov, Zdeněk Havlas, Josef Michl, Noa Marom. Inverse Design of Tetracene Polymorphs with Enhanced Singlet Fission Performance by Property-Based Genetic Algorithm Optimization. Chemistry of Materials 2023, 35 (3) , 1373-1386. https://doi.org/10.1021/acs.chemmater.2c03444
    4. Alastair J. A. Price, Alberto Otero-de-la-Roza, Erin R. Johnson. XDM-corrected hybrid DFT with numerical atomic orbitals predicts molecular crystal lattice energies with unprecedented accuracy. Chemical Science 2023, 14 (5) , 1252-1262. https://doi.org/10.1039/D2SC05997E

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