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A Bond-Energy/Bond-Order and Populations Relationship

  • Barbaro Zulueta
    Barbaro Zulueta
    Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
  • Sonia V. Tulyani
    Sonia V. Tulyani
    Formerly Chemical Engineering Department, University of Massachusetts Amherst,618 North Pleasant Street, Amherst, Massachusetts 01003, United States
  • Phillip R. Westmoreland
    Phillip R. Westmoreland
    Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27695, United States
  • Michael J. Frisch
    Michael J. Frisch
    Gaussian, Inc., Wallingford, Connecticut 06492, United States
  • E. James Petersson
    E. James Petersson
    Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
  • George A. Petersson
    George A. Petersson
    Institute for Computational Molecular Science, Temple University, Philadelphia, Pennsylvania 19122, United States
    Formerly Hall-Atwater Laboratories of Chemistry, Wesleyan University, Middletown, Connecticut 06459, United States
  • , and 
  • John A. Keith*
    John A. Keith
    Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
    *Email: [email protected]
Cite this: J. Chem. Theory Comput. 2022, 18, 8, 4774–4794
Publication Date (Web):July 18, 2022
https://doi.org/10.1021/acs.jctc.2c00334
Copyright © 2022 American Chemical Society

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    Abstract

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    We report an analytical bond energy from bond orders and populations (BEBOP) model that provides intramolecular bond energy decompositions for chemical insight into the thermochemistry of molecules. The implementation reported here employs a minimum basis set Mulliken population analysis on well-conditioned Hartree–Fock orbitals to decompose total electronic energies into physically interpretable contributions. The model’s parametrization scheme is based on atom-specific parameters for hybridization and atom pair-specific parameters for short-range repulsion and extended Hückel-type bond energy term fitted to reproduce CBS-QB3 thermochemistry data. The current implementation is suitable for molecules involving H, Li, Be, B, C, N, O, and F atoms, and it can be used to analyze intramolecular bond energies of molecular structures at optimized stationary points found from other computational methods. This first-generation model brings the computational cost of a Hartree–Fock calculation using a large triple-ζ basis set, and its atomization energies are comparable to those from widely used hybrid Kohn–Sham density functional theory (DFT, as benchmarked to 109 species from the G2/97 test set and an additional 83 reference species). This model should be useful for the community by interpreting overall ab initio molecular energies in terms of physically insightful bond energy contributions, e.g., bond dissociation energies, resonance energies, molecular strain energies, and qualitative energetic contributions to the activation barrier in chemical reaction mechanisms. This work reports a critical benchmarking of this method as well as discussions of its strengths and weaknesses compared to hybrid DFT (i.e., B3LYP, M062X, PBE0, and APF methods), and other cost-effective approximate Hamiltonian semiempirical quantum methods (i.e., AM1, PM6, PM7, and DFTB3).

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jctc.2c00334.

    • Derivation of the extended-Hückel theory and data for trigonal planar and trigonal pyramidal NH3 (PDF)

    • Excel file of all computed data (XLSX)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 2 publications.

    1. Dan Hong, Wei Zeng, Zheng-Tang Liu, Fu-Sheng Liu, Qi-Jun Liu. Initial Decomposition of DATB Induced by an External Electric Field. The Journal of Physical Chemistry A 2023, 127 (24) , 5140-5151. https://doi.org/10.1021/acs.jpca.3c01298
    2. Michael J. Sahre, Guido Falk von Rudorff, O. Anatole von Lilienfeld. Quantum Alchemy Based Bonding Trends and Their Link to Hammett’s Equation and Pauling’s Electronegativity Model. Journal of the American Chemical Society 2023, 145 (10) , 5899-5908. https://doi.org/10.1021/jacs.2c13393

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