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Title: Development of a Multicenter Density Functional Tight Binding Model for Plutonium Surface Hydriding [Development of a Many-Body Density Functional Tight Binding Model for Plutonium Surface Hydriding]

We detail the creation of a multicenter density functional tight binding (DFTB) model for hydrogen on δ-plutonium, using a framework of new Slater-Koster interaction parameters and a repulsive energy based on the Chebyshev Interaction Model for Efficient Simulation (ChIMES), where two- and three-center atomic interactions are represented by linear combinations of Chebyshev polynomials. Here, we find that our DFTB/ChIMES model yields a total electron density of states for bulk δ-Pu that compares well to that from Density Functional Theory, as well as to a grid of energy calculations representing approximate H 2 dissociation paths on the δ-Pu (100) surface. We then perform molecular dynamics simulations and minimum energy pathway calculations to determine the energetics of surface dissociation and subsurface diffusion on the (100) and (111) surfaces. Our approach allows for the efficient creation of multicenter repulsive energies with a relatively small investment in initial DFT calculations. Lastly, our efforts are particularly pertinent to studies that rely on quantum calculations for interpretation and validation, such as experimental determination of chemical reactivity both on surfaces and in condensed phases.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [3] ;  [3]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate; Univ. of California, Davis, CA (United States). Dept. of Chemical Engineering
  2. Univ. of Bremen (Germany). Bremen Center for Computational Materials Science
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
Publication Date:
Report Number(s):
LLNL-JRNL-746090
Journal ID: ISSN 1549-9618; 930532
Grant/Contract Number:
AC52-07NA27344
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 14; Journal Issue: 5; Journal ID: ISSN 1549-9618
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
OSTI Identifier:
1466952

Goldman, Nir, Aradi, Bálint, Lindsey, Rebecca K., and Fried, Laurence E.. Development of a Multicenter Density Functional Tight Binding Model for Plutonium Surface Hydriding [Development of a Many-Body Density Functional Tight Binding Model for Plutonium Surface Hydriding]. United States: N. p., Web. doi:10.1021/acs.jctc.8b00165.
Goldman, Nir, Aradi, Bálint, Lindsey, Rebecca K., & Fried, Laurence E.. Development of a Multicenter Density Functional Tight Binding Model for Plutonium Surface Hydriding [Development of a Many-Body Density Functional Tight Binding Model for Plutonium Surface Hydriding]. United States. doi:10.1021/acs.jctc.8b00165.
Goldman, Nir, Aradi, Bálint, Lindsey, Rebecca K., and Fried, Laurence E.. 2018. "Development of a Multicenter Density Functional Tight Binding Model for Plutonium Surface Hydriding [Development of a Many-Body Density Functional Tight Binding Model for Plutonium Surface Hydriding]". United States. doi:10.1021/acs.jctc.8b00165. https://www.osti.gov/servlets/purl/1466952.
@article{osti_1466952,
title = {Development of a Multicenter Density Functional Tight Binding Model for Plutonium Surface Hydriding [Development of a Many-Body Density Functional Tight Binding Model for Plutonium Surface Hydriding]},
author = {Goldman, Nir and Aradi, Bálint and Lindsey, Rebecca K. and Fried, Laurence E.},
abstractNote = {We detail the creation of a multicenter density functional tight binding (DFTB) model for hydrogen on δ-plutonium, using a framework of new Slater-Koster interaction parameters and a repulsive energy based on the Chebyshev Interaction Model for Efficient Simulation (ChIMES), where two- and three-center atomic interactions are represented by linear combinations of Chebyshev polynomials. Here, we find that our DFTB/ChIMES model yields a total electron density of states for bulk δ-Pu that compares well to that from Density Functional Theory, as well as to a grid of energy calculations representing approximate H2 dissociation paths on the δ-Pu (100) surface. We then perform molecular dynamics simulations and minimum energy pathway calculations to determine the energetics of surface dissociation and subsurface diffusion on the (100) and (111) surfaces. Our approach allows for the efficient creation of multicenter repulsive energies with a relatively small investment in initial DFT calculations. Lastly, our efforts are particularly pertinent to studies that rely on quantum calculations for interpretation and validation, such as experimental determination of chemical reactivity both on surfaces and in condensed phases.},
doi = {10.1021/acs.jctc.8b00165},
journal = {Journal of Chemical Theory and Computation},
number = 5,
volume = 14,
place = {United States},
year = {2018},
month = {4}
}