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Quantum monte carlo study of heats of formation and bond dissociation energies of small hydrocarbons

Authors

  • A. C. Kollias,

    1. Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460
    2. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
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  • D. Domin,

    1. Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460
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  • G. Hill,

    1. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
    2. Computational Center for Molecular Structure and Interactions, Jackson State University, Jackson, MS 39217
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  • M. Frenklach,

    1. Department of Mechanical Engineering, University of California at Berkeley, Berkeley, CA 94720-1740
    2. Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
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  • D. M. Golden,

    1. Department of Mechanical Engineering, Stanford University, Stanford, CA 94305
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  • W. A. Lester Jr.

    Corresponding author
    1. Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460
    2. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
    • Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
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Abstract

A quantum Monte Carlo (QMC) benchmark study of heats of formation at 298 K and bond dissociation energies (BDEs) of 22 small hydrocarbons is reported. Diffusion Monte Carlo (DMC) results, obtained using a simple product trial wavefunctions consisting of a single determinant and correlation function, are compared to experiment and to other theory including a version of complete basis set theory (CBS-Q) and density functional theory (DFT) with the B3LYP functional. For heats of formation, the findings are a mean absolute deviation from experiment of 1.2 kcal/mol for CBS-Q, 2.0 kcal/mol for B3LYP, and 2.2 kcal/mol for DMC. The mean absolute deviation of 31 BDEs is 2.0 kcal/mol for CBS-Q, 4.2 kcal/mol for B3LYP, and 2.5 kcal/mol for DMC. These findings are for 17 BDEs of closed-shell molecules that have mean absolute deviations from experiment of 1.7 kcal/mol (CBS-Q), 4.0 kcal/mol (B3LYP), and 2.2 kcal/mol (DMC). The corresponding results for the 14 BDEs of open-shell molecules studied are 2.4 kcal/mol (CBS-Q), 4.3 kcal/mol (B3LYP), and 2.9 kcal/mol (DMC). The DMC results provide a baseline from which improvement using multideterminant trial functions can be measured. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 583–592, 2005

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