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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 in this study. 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]
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  1. Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States). Dept. of Physics
Publication Date:
Research Org.:
Univ. of Illinois at Urbana-Champaign, Urbana, 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:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 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. Wed . "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 in this study. 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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