A Bond-Energy/Bond-Order and Populations Relationship

• Published in: Journal of chemical theory and computation Vol. 18; no. 8; pp. 4774 - 4794
• Main Authors: Zulueta, Barbaro, Tulyani, Sonia V., Westmoreland, Phillip R., Frisch, Michael J., Petersson, E. James, Petersson, George A., Keith, John A.
• Format: Journal Article
• Language: English
• Published: Washington American Chemical Society 09.08.2022
• Subjects: Atomizing; Bond energy; Chemical bonds; Chemical reactions; Computing costs; Decomposition; Density functional theory; Hartree approximation; Mathematical models; Molecular structure; Parameterization; Parameters; Populations; Quantum Electronic Structure; Reaction mechanisms; Thermochemistry
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.2c00334

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).