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Title: Insights on the Alumina–Water Interface Structure by Direct Comparison of Density Functional Simulations with X-ray Reflectivity

Abstract

Density functional theory molecular dynamics (DFT-MD) simulations are frequently used to predict the interfacial structures and dynamical processes at solid-water interfaces in efforts to gain a deeper understanding of these systems. However, the accuracy of these predictions of interfacial structure has not been rigorously quantified. Here, direct comparisons between large-scale DFT-MD simulations and high-resolution X-ray reflectivity (XR) measurements of the well-defined Al2O3(001)-water interface reveal the relative accuracy of these two methods to describe interfacial structure, a comparison that is enabled by XR’s high sensitivity to atomic-scale displacements. The DFT-MD simulated and XR model-fit structures are qualitatively similar, but XR signals calculated directly from the DFT-MD predictions deviate significantly from the experimental data, revealing discrepancies in these two approaches. Differences in the derived interfacial Al2O3 relaxation profiles of ~0.02 A within the top 5 layers are significant to XR but at the limit of the accuracy of DFT. Further differences are found in the surface hydration layer with a simulated average water layer height ~0.2 A higher than that observed experimentally. This is outside the accuracy of both XR and DFT and is not improved by the inclusion of a phenomenological correction for hydrogen bonding (e.g., Grimme).

Authors:
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [1];  [2]; ORCiD logo [5]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States)
  2. Univ. of California San Diego, La Jolla, CA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Washington Univ., St. Louis, MO (United States)
  5. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1493757
Alternate Identifier(s):
OSTI ID: 1489266
Report Number(s):
PNNL-SA-138269
Journal ID: ISSN 1932-7447; 146384
Grant/Contract Number:  
AC02-06CH11357; AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 47; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ab initio molecular dynamics; alumina-water interface; crystal truncation rod; interfacial water structure; Ab Initio Molecular Dynamics, Crystal Truncation Rod, Alumina-Water Interface, Interfacial Water Structure

Citation Formats

Harmon, Katherine J., Chen, Ying, Bylaska, Eric J., Catalano, Jeffrey G., Bedzyk, Michael J., Weare, John H., and Fenter, Paul. Insights on the Alumina–Water Interface Structure by Direct Comparison of Density Functional Simulations with X-ray Reflectivity. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b08522.
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Harmon, Katherine J., Chen, Ying, Bylaska, Eric J., Catalano, Jeffrey G., Bedzyk, Michael J., Weare, John H., & Fenter, Paul. Insights on the Alumina–Water Interface Structure by Direct Comparison of Density Functional Simulations with X-ray Reflectivity. United States. https://doi.org/10.1021/acs.jpcc.8b08522
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Harmon, Katherine J., Chen, Ying, Bylaska, Eric J., Catalano, Jeffrey G., Bedzyk, Michael J., Weare, John H., and Fenter, Paul. Wed . "Insights on the Alumina–Water Interface Structure by Direct Comparison of Density Functional Simulations with X-ray Reflectivity". United States. https://doi.org/10.1021/acs.jpcc.8b08522. https://www.osti.gov/servlets/purl/1493757.
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@article{osti_1493757,
title = {Insights on the Alumina–Water Interface Structure by Direct Comparison of Density Functional Simulations with X-ray Reflectivity},
author = {Harmon, Katherine J. and Chen, Ying and Bylaska, Eric J. and Catalano, Jeffrey G. and Bedzyk, Michael J. and Weare, John H. and Fenter, Paul},
abstractNote = {Density functional theory molecular dynamics (DFT-MD) simulations are frequently used to predict the interfacial structures and dynamical processes at solid-water interfaces in efforts to gain a deeper understanding of these systems. However, the accuracy of these predictions of interfacial structure has not been rigorously quantified. Here, direct comparisons between large-scale DFT-MD simulations and high-resolution X-ray reflectivity (XR) measurements of the well-defined Al2O3(001)-water interface reveal the relative accuracy of these two methods to describe interfacial structure, a comparison that is enabled by XR’s high sensitivity to atomic-scale displacements. The DFT-MD simulated and XR model-fit structures are qualitatively similar, but XR signals calculated directly from the DFT-MD predictions deviate significantly from the experimental data, revealing discrepancies in these two approaches. Differences in the derived interfacial Al2O3 relaxation profiles of ~0.02 A within the top 5 layers are significant to XR but at the limit of the accuracy of DFT. Further differences are found in the surface hydration layer with a simulated average water layer height ~0.2 A higher than that observed experimentally. This is outside the accuracy of both XR and DFT and is not improved by the inclusion of a phenomenological correction for hydrogen bonding (e.g., Grimme).},
doi = {10.1021/acs.jpcc.8b08522},
journal = {Journal of Physical Chemistry. C},
number = 47,
volume = 122,
place = {United States},
year = {Wed Oct 17 00:00:00 EDT 2018},
month = {Wed Oct 17 00:00:00 EDT 2018}
}
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Journal Article:
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https://doi.org/10.1021/acs.jpcc.8b08522
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Figures / Tables:

Figure 1 Figure 1: (A) Snapshot of the Al2O3(001)/water system from the PBE-based DFT-MD simulation is shown with the supercell perpendicular to the alumina (001) surface indicated by the white box. The vertical dashed line (at left) coincides with the alumina slab center at z = 0 in (B). The O atomsmore » are red, Al atoms are pink, and H atoms are white. (B) An overlay of O atom positions in alumina from the DFT calculations of the bulk alumina structure at 0 K and at 300 K and from the hydrated DFT-MD alumina slab reveals a small but significant expansion of O spacing upon solvation. Peaks at ±15 Å in the DFT-MD plot (blue) are the start of the water profile.« less
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