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American Institute of Physics, The Journal of Chemical Physics, 12(146), p. 124129

DOI: 10.1063/1.4979059

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Accurate barrier heights using diffusion Monte Carlo

Journal article published in 2016 by Kittithat Krongchon ORCID, Brian Busemeyer ORCID, Lucas K. Wagner ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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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(5) 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 correlate with the gap between the highest occupied and lowest unoccupied orbital energies in the mean-field calculation. ; Comment: 6 pages, 4 figures, 1 table