Development of a Multicenter Density Functional Tight Binding Model for Plutonium Surface Hydriding [Development of a ManyBody 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 δplutonium, using a framework of new SlaterKoster interaction parameters and a repulsive energy based on the Chebyshev Interaction Model for Efficient Simulation (ChIMES), where two and threecenter 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 δPu 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 δPu (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:

^{[1]}
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;
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 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
 Univ. of Bremen (Germany). Bremen Center for Computational Materials Science
 Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
 Publication Date:
 Report Number(s):
 LLNLJRNL746090
Journal ID: ISSN 15499618; 930532
 Grant/Contract Number:
 AC5207NA27344
 Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Theory and Computation
 Additional Journal Information:
 Journal Volume: 14; Journal Issue: 5; Journal ID: ISSN 15499618
 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 ManyBody 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 ManyBody 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 ManyBody 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 ManyBody 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 δplutonium, using a framework of new SlaterKoster interaction parameters and a repulsive energy based on the Chebyshev Interaction Model for Efficient Simulation (ChIMES), where two and threecenter 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 δPu 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 δPu (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}
}