Research Article

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

  1. A. C. Kollias1,2,
  2. D. Domin1,
  3. G. Hill2,3,
  4. M. Frenklach4,5,
  5. D. M. Golden6,
  6. W. A. Lester Jr.1,2,*

Article first published online: 22 AUG 2005

DOI: 10.1002/kin.20063

Issue

International Journal of Chemical Kinetics

International Journal of Chemical Kinetics

Volume 37, Issue 10, pages 583–592, October 2005

Additional Information

How to Cite

Kollias, A. C., Domin, D., Hill, G., Frenklach, M., Golden, D. M. and Lester, W. A. (2005), Quantum monte carlo study of heats of formation and bond dissociation energies of small hydrocarbons. Int. J. Chem. Kinet., 37: 583–592. doi: 10.1002/kin.20063

Author Information

  1. 1

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

  2. 2

    Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720

  3. 3

    Computational Center for Molecular Structure and Interactions, Jackson State University, Jackson, MS 39217

  4. 4

    Department of Mechanical Engineering, University of California at Berkeley, Berkeley, CA 94720-1740

  5. 5

    Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720

  6. 6

    Department of Mechanical Engineering, Stanford University, Stanford, CA 94305

*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

Publication History

  1. Issue published online: 22 AUG 2005
  2. Article first published online: 22 AUG 2005
  3. Manuscript Accepted: 5 OCT 2004
  4. Manuscript Received: 8 SEP 2004

Funded by

  • Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences Division of the U.S. Department of Energy. Grant Number: DE-AC03-76SF00098
  • CREST Program of the National Science Foundation. Grant Number: HRD0318519
  • Director, Office of Science, Office of Basic Energy Sciences, Environmental Energy Technologies Division of the U.S. Department of Energy. Grant Number: DE-AC03-76SF00098
  • The Global Climate and Energy program at Stanford University

SEARCH

SEARCH BY CITATION

ARTICLE TOOLS

View Full Article (HTML) Get PDF (125K)

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

View Full Article (HTML) Get PDF (125K)