Accurate barrier heights using diffusion Monte Carlo

doi:10.1063/1.4979059

Title: Accurate barrier heights using diffusion Monte Carlo

Abstract

Fixed node diffusion Monte Carlo (DMC) has been performed on a test set of forward and reverse barrier heights for 19 non-hydrogen-transfer reactions, and the nodal error has been assessed. The DMC results are robust to changes in the nodal surface, as assessed by using different mean-field techniques to generate single determinant wave functions. Using these single determinant nodal surfaces, DMC results in errors of 1.5(1) kcal/mol on barrier heights. Using the large data set of DMC energies, we attempted to find good descriptors of the fixed node error. It does not correlate with a number of descriptors including change in density but does show some correlation with the gap between the highest occupied and lowest unoccupied orbital energies in the mean-field calculation.

Authors:

^[1];

^[1]

Department of Physics, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA

Publication Date:: 2017-03-28

Research Org.:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1535305

Grant/Contract Number:: SC0008692

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 146; Journal Issue: 12; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: Chemistry; Physics

Citation Formats


                    Krongchon, Kittithat, Busemeyer, Brian, and Wagner, Lucas K. Accurate barrier heights using diffusion Monte Carlo.  United States: N. p., 2017. 
        Web.  doi:10.1063/1.4979059.

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                    Krongchon, Kittithat, Busemeyer, Brian, & Wagner, Lucas K. Accurate barrier heights using diffusion Monte Carlo.  United States.  doi:10.1063/1.4979059.

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                    Krongchon, Kittithat, Busemeyer, Brian, and Wagner, Lucas K. Tue .  
        "Accurate barrier heights using diffusion Monte Carlo".  United States.  doi:10.1063/1.4979059.  https://www.osti.gov/servlets/purl/1535305.

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@article{osti_1535305,

  title        = {Accurate barrier heights using diffusion Monte Carlo},

  author       = {Krongchon, Kittithat and Busemeyer, Brian and Wagner, Lucas K.},

  abstractNote = {Fixed node diffusion Monte Carlo (DMC) has been performed on a test set of forward and reverse barrier heights for 19 non-hydrogen-transfer reactions, and the nodal error has been assessed. The DMC results are robust to changes in the nodal surface, as assessed by using different mean-field techniques to generate single determinant wave functions. Using these single determinant nodal surfaces, DMC results in errors of 1.5(1) kcal/mol on barrier heights. Using the large data set of DMC energies, we attempted to find good descriptors of the fixed node error. It does not correlate with a number of descriptors including change in density but does show some correlation with the gap between the highest occupied and lowest unoccupied orbital energies in the mean-field calculation.},

  doi          = {10.1063/1.4979059},

  journal      = {Journal of Chemical Physics},

  number       = 12,

  volume       = 146,

  place        = {United States},

  year         = {2017},

  month        = {3}

}

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DOI: 10.1063/1.4979059

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
DOI: 10.1103/PhysRevLett.77.3865

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Title: Accurate barrier heights using diffusion Monte Carlo

Abstract

Citation Formats

Generalized Gradient Approximation Made Simple journal, October 1996

Generalized Gradient Approximation Made Simple
journal, October 1996