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Title: The role of decomposition reactions in assessing first-principles predictions of solid stability

Abstract

Here, the performance of density functional theory approximations for predicting materials thermodynamics is typically assessed by comparing calculated and experimentally determined enthalpies of formation from elemental phases, ΔH f. However, a compound competes thermodynamically with both other compounds and their constituent elemental forms, and thus, the enthalpies of the decomposition reactions to these competing phases, ΔH d, determine thermodynamic stability. We evaluated the phase diagrams for 56,791 compounds to classify decomposition reactions into three types: 1. those that produce elemental phases, 2. those that produce compounds, and 3. those that produce both. This analysis shows that the decomposition into elemental forms is rarely the competing reaction that determines compound stability and that approximately two-thirds of decomposition reactions involve no elemental phases. Using experimentally reported formation enthalpies for 1012 solid compounds, we assess the accuracy of the generalized gradient approximation (GGA) (PBE) and meta-GGA (SCAN) density functionals for predicting compound stability.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]
  1. Univ. of Colorado, Boulder, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1492518
Report Number(s):
NREL/JA-5K00-73187
Journal ID: ISSN 2057-3960
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
npj Computational Materials
Additional Journal Information:
Journal Volume: 5; Journal Issue: 1; Journal ID: ISSN 2057-3960
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; density functional theory; thermodynamics; decomposition

Citation Formats

Bartel, Christopher J., Weimer, Alan W., Lany, Stephan, Musgrave, Charles B., and Holder, Aaron M. The role of decomposition reactions in assessing first-principles predictions of solid stability. United States: N. p., 2019. Web. doi:10.1038/s41524-018-0143-2.
Bartel, Christopher J., Weimer, Alan W., Lany, Stephan, Musgrave, Charles B., & Holder, Aaron M. The role of decomposition reactions in assessing first-principles predictions of solid stability. United States. doi:10.1038/s41524-018-0143-2.
Bartel, Christopher J., Weimer, Alan W., Lany, Stephan, Musgrave, Charles B., and Holder, Aaron M. Fri . "The role of decomposition reactions in assessing first-principles predictions of solid stability". United States. doi:10.1038/s41524-018-0143-2. https://www.osti.gov/servlets/purl/1492518.
@article{osti_1492518,
title = {The role of decomposition reactions in assessing first-principles predictions of solid stability},
author = {Bartel, Christopher J. and Weimer, Alan W. and Lany, Stephan and Musgrave, Charles B. and Holder, Aaron M.},
abstractNote = {Here, the performance of density functional theory approximations for predicting materials thermodynamics is typically assessed by comparing calculated and experimentally determined enthalpies of formation from elemental phases, ΔHf. However, a compound competes thermodynamically with both other compounds and their constituent elemental forms, and thus, the enthalpies of the decomposition reactions to these competing phases, ΔHd, determine thermodynamic stability. We evaluated the phase diagrams for 56,791 compounds to classify decomposition reactions into three types: 1. those that produce elemental phases, 2. those that produce compounds, and 3. those that produce both. This analysis shows that the decomposition into elemental forms is rarely the competing reaction that determines compound stability and that approximately two-thirds of decomposition reactions involve no elemental phases. Using experimentally reported formation enthalpies for 1012 solid compounds, we assess the accuracy of the generalized gradient approximation (GGA) (PBE) and meta-GGA (SCAN) density functionals for predicting compound stability.},
doi = {10.1038/s41524-018-0143-2},
journal = {npj Computational Materials},
number = 1,
volume = 5,
place = {United States},
year = {2019},
month = {1}
}

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Cited by: 5 works
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Figures / Tables:

Figure 1 Figure 1: Three unique decomposition reactions A stable (top) and metastable (bottom) example of each reaction type. Left: reaction Type 1— the decomposition products are the elements; center: reaction Type 2—the decomposition products contain no elements; right: reaction Type 3—the decomposition products contain elements and compounds. Solid blue circles aremore » breaks in the hull (stable) and open red triangles are above the hull (metastable). In all examples, A and B are arbitrary elements. We note that in the stable Type 2 example (top center), the stability of AB is determined by a stable compound, AB2, and an unstable compound, A3B2. This particular phase diagram is chosen to emphasize that the decomposition of stable compounds can include unstable compounds« less

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