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Title: Introduction to First-Principles Electronic Structure Methods: Application to Actinide Materials

Abstract

This paper provides an introduction for non-experts to first-principles electronic structure methods that are widely used in condensed-matter physics. Particular emphasis is placed on giving the appropriate background information needed to better appreciate the use of these methods to study actinide and other materials. Specifically, I describe the underlying theory sufficiently to enable an understanding of the relative strengths and weaknesses of the methods. I also explain the meaning of commonly used terminology, including density functional theory (DFT), local density approximation (LDA), and generalized gradient approximation (GGA), as well as linear muffin-tin orbital (LMTO), linear augmented plane wave (LAPW), and pseudopotential methods. I also briefly discuss methodologies that extend the basic theory to address specific limitations. Finally, I describe a few illustrative applications, including quantum molecular dynamics (QMD) simulations and studies of surfaces, impurities, and defects. I conclude by addressing the current controversy regarding magnetic calculations for actinide materials.

Authors:
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
899388
Report Number(s):
UCRL-JRNL-221153
TRN: US0701955
DOE Contract Number:
W-7405-ENG-48
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Materials Research, vol. 21, no. 12, December 1, 2006, pp. 2979-2985
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ACTINIDES; APPROXIMATIONS; DEFECTS; ELECTRONIC STRUCTURE; FUNCTIONALS; IMPURITIES; PHYSICS

Citation Formats

Klepeis, J E. Introduction to First-Principles Electronic Structure Methods: Application to Actinide Materials. United States: N. p., 2006. Web. doi:10.1557/jmr.2006.0371.
Klepeis, J E. Introduction to First-Principles Electronic Structure Methods: Application to Actinide Materials. United States. doi:10.1557/jmr.2006.0371.
Klepeis, J E. Fri . "Introduction to First-Principles Electronic Structure Methods: Application to Actinide Materials". United States. doi:10.1557/jmr.2006.0371. https://www.osti.gov/servlets/purl/899388.
@article{osti_899388,
title = {Introduction to First-Principles Electronic Structure Methods: Application to Actinide Materials},
author = {Klepeis, J E},
abstractNote = {This paper provides an introduction for non-experts to first-principles electronic structure methods that are widely used in condensed-matter physics. Particular emphasis is placed on giving the appropriate background information needed to better appreciate the use of these methods to study actinide and other materials. Specifically, I describe the underlying theory sufficiently to enable an understanding of the relative strengths and weaknesses of the methods. I also explain the meaning of commonly used terminology, including density functional theory (DFT), local density approximation (LDA), and generalized gradient approximation (GGA), as well as linear muffin-tin orbital (LMTO), linear augmented plane wave (LAPW), and pseudopotential methods. I also briefly discuss methodologies that extend the basic theory to address specific limitations. Finally, I describe a few illustrative applications, including quantum molecular dynamics (QMD) simulations and studies of surfaces, impurities, and defects. I conclude by addressing the current controversy regarding magnetic calculations for actinide materials.},
doi = {10.1557/jmr.2006.0371},
journal = {Journal of Materials Research, vol. 21, no. 12, December 1, 2006, pp. 2979-2985},
number = ,
volume = ,
place = {United States},
year = {Fri May 05 00:00:00 EDT 2006},
month = {Fri May 05 00:00:00 EDT 2006}
}
  • The purpose of this paper is to provide an introduction for non-experts to first-principles electronic structure methods that are widely used in the field of condensed-matter physics, including applications to actinide materials. The methods I describe are based on density functional theory (DFT) within the local density approximation (LDA) and the generalized gradient approximation (GGA). In addition to explaining the meaning of this terminology I also describe the underlying theory itself in some detail in order to enable a better understanding of the relative strengths and weaknesses of the methods. I briefly mention some particular numerical implementations of DFT, includingmore » the linear muffin-tin orbital (LMTO), linear augmented plane wave (LAPW), and pseudopotential methods, as well as general methodologies that go beyond DFT and specifically address some of the weaknesses of the theory. The last third of the paper is devoted to a few selected applications that illustrate the ideas discussed in the first two-thirds. In particular, I conclude by addressing the current controversy regarding magnetic DFT calculations for actinide materials. Throughout this paper particular emphasis is placed on providing the appropriate background to enable the non-expert to gain a better appreciation of the application of first-principles electronic structure methods to the study of actinide and other materials.« less
  • The ground-state electronic structures of the actinide oxides AO, A{sub 2}O{sub 3}, and AO{sub 2} (A=U, Np, Pu, Am, Cm, Bk, and Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density approximation. Emphasis is put on the degree of f-electron localization, which for AO{sub 2} and A{sub 2}O{sub 3} is found to follow the stoichiometry, namely, corresponding to A{sup 4+} ions in the dioxide and A{sup 3+} ions in the sesquioxides. In contrast, the A{sup 2+} ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics of the oxidation and reduction in themore » actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onward. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground-state configurations of the corresponding lanthanide oxides. The ionic nature of the actinide oxides emerges from the fact that only those compounds will form where the calculated ground-state valency agrees with the nominal valency expected from a simple charge counting.« less
  • The ground-state electronic structures of the actinide oxides AO , A 2 O 3 , and AO 2 (A=U , Np, Pu, Am, Cm, Bk, and Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density approximation. Emphasis is put on the degree of f -electron localization, which for AO 2 and A 2 O 3 is found to follow the stoichiometry, namely, corresponding to A 4+ ions in the dioxide and A 3+ ions in the sesquioxides. In contrast, the A 2+ ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics ofmore » the oxidation and reduction in the actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onward. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground-state configurations of the corresponding lanthanide oxides. The ionic nature of the actinide oxides emerges from the fact that only those compounds will form where the calculated ground-state valency agrees with the nominal valency expected from a simple charge counting.« less