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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:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Physics, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
Publication Date:
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.
Krongchon, Kittithat, Busemeyer, Brian, & Wagner, Lucas K. Accurate barrier heights using diffusion Monte Carlo. United States. doi:10.1063/1.4979059.
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.
@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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Cited by: 4 works
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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
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