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Title: A First-Principles Study of Hydrogen Diffusivity and Dissociation on δ-Pu (100) and (111) Surfaces

The diffusivity and chemical reactivity of hydrogen on the δ-Pu (100) and (111) surfaces has been studied with density functional theory using both spin-polarization and spin–orbit coupling calculations. Comparison of the total electronic density of states and atomic hydrogen diffusion energies indicates that spin-polarization yields accurate results, with spin–orbit coupling yielding slightly smaller barriers to hopping between adsorption sites. On the (100) surface, both sets of calculations indicate that the dissociation reaction for molecular hydrogen is highly active at ambient conditions and results in the hydrogen ions bonded within the Pu surface, similar to hydride formation. In contrast, calculations on the (111) surface indicate a lower barrier for dissociation without the formation of the hydride-like end product. Our results help quantify the effect of spin–orbit coupling on hydrogen surface chemistry on δ-Pu. Additionally, we observe that the degree of resulting corrosion could depend on the specific geometry of the plutonium surface, which could have ramifications for future engineering applications.
Authors:
ORCiD logo [1] ;  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Report Number(s):
LLNL-JRNL-731689
Journal ID: ISSN 1932-7447; 881850
Grant/Contract Number:
AC52-07NA27344
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 33; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1466930

Goldman, Nir, and Morales, Miguel A. A First-Principles Study of Hydrogen Diffusivity and Dissociation on δ-Pu (100) and (111) Surfaces. United States: N. p., Web. doi:10.1021/acs.jpcc.7b04992.
Goldman, Nir, & Morales, Miguel A. A First-Principles Study of Hydrogen Diffusivity and Dissociation on δ-Pu (100) and (111) Surfaces. United States. doi:10.1021/acs.jpcc.7b04992.
Goldman, Nir, and Morales, Miguel A. 2017. "A First-Principles Study of Hydrogen Diffusivity and Dissociation on δ-Pu (100) and (111) Surfaces". United States. doi:10.1021/acs.jpcc.7b04992. https://www.osti.gov/servlets/purl/1466930.
@article{osti_1466930,
title = {A First-Principles Study of Hydrogen Diffusivity and Dissociation on δ-Pu (100) and (111) Surfaces},
author = {Goldman, Nir and Morales, Miguel A.},
abstractNote = {The diffusivity and chemical reactivity of hydrogen on the δ-Pu (100) and (111) surfaces has been studied with density functional theory using both spin-polarization and spin–orbit coupling calculations. Comparison of the total electronic density of states and atomic hydrogen diffusion energies indicates that spin-polarization yields accurate results, with spin–orbit coupling yielding slightly smaller barriers to hopping between adsorption sites. On the (100) surface, both sets of calculations indicate that the dissociation reaction for molecular hydrogen is highly active at ambient conditions and results in the hydrogen ions bonded within the Pu surface, similar to hydride formation. In contrast, calculations on the (111) surface indicate a lower barrier for dissociation without the formation of the hydride-like end product. Our results help quantify the effect of spin–orbit coupling on hydrogen surface chemistry on δ-Pu. Additionally, we observe that the degree of resulting corrosion could depend on the specific geometry of the plutonium surface, which could have ramifications for future engineering applications.},
doi = {10.1021/acs.jpcc.7b04992},
journal = {Journal of Physical Chemistry. C},
number = 33,
volume = 121,
place = {United States},
year = {2017},
month = {7}
}