Accurate Bond Energies of Hydrocarbons from Complete Basis Set Extrapolated Multi-Reference Singles and Doubles Configuration Interaction

Authors

  • Victor B. Oyeyemi,

    1. Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey, 08544-5263 (USA), Fax: (+1) 609 258 5877
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  • Dr. Michele Pavone,

    1. Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey, 08544-5263 (USA)
    2. Permanent address: Department of Chemistry, University of Napoli Federico II, Napoli 80120 (Italy)
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  • Prof. Dr. Emily A. Carter

    Corresponding author
    1. Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey, 08544-5263 (USA)
    2. Program in Applied and Computational Mathematics, Princeton University, Princeton, New Jersey, 08544 (USA)
    3. Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey, 08544-5263 (USA)
    • Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey, 08544-5263 (USA)
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Abstract

Quantum chemistry has become one of the most reliable tools for characterizing the thermochemical underpinnings of reactions, such as bond dissociation energies (BDEs). The accurate prediction of these particular properties (BDEs) are challenging for ab initio methods based on perturbative corrections or coupled cluster expansions of the single-determinant Hartree–Fock wave function: the processes of bond breaking and forming are inherently multi-configurational and require an accurate description of non-dynamical electron correlation. To this end, we present a systematic ab initio approach for computing BDEs that is based on three components: 1) multi-reference single and double excitation configuration interaction (MRSDCI) for the electronic energies; 2) a two-parameter scheme for extrapolating MRSDCI energies to the complete basis set limit; and 3) DFT-B3LYP calculations of minimum-energy structures and vibrational frequencies to account for zero point energy and thermal corrections. We validated our methodology against a set of reliable experimental BDE values of C[BOND]C and C[BOND]H bonds of hydrocarbons. The goal of chemical accuracy is achieved, on average, without applying any empirical corrections to the MRSDCI electronic energies. We then use this composite scheme to make predictions of BDEs in a large number of hydrocarbon molecules for which there are no experimental data, so as to provide needed thermochemical estimates for fuel molecules.

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