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Title: Ab Initio Molecular Dynamics Reveal Spectroscopic Siblings and Ion Pairing as New Challenges for Elucidating Prenucleation Aluminum Speciation

Abstract

We report the characterization of prenucleation species is essential to understand crystallization mechanisms across many chemical systems and often involves the use of vibrational spectroscopy. Nowhere is this more evident than in the development of “green” aluminum processing technologies, where detailed understanding of the speciation of aluminum and its polynuclear analogues in highly alkaline, low water solutions is elusive. The aluminate anion Al(OH)4– predominates in alkaline conditions, yet equilibrium with dimeric species, either μ-oxo Al2O(OH)62– or di-μ-hydroxo Al2(OH)82–, can be assumed. Using ab initio molecular dynamics with full solvation and the presence of counterions, this work reconciles previous contradictory studies that had concluded only a single species under relevant solution conditions. We reveal that the two dimers are energetically separated by 2 kcal/mol in pure water but that the stability of each can be reversed by ion pairing expected in saturated salt solutions. Simulated Raman and IR spectra for each species (accounting for anharmonicity and the fluctuating solvating environment) provide the first proof that the considered species are “spectroscopic siblings”, whose multiple overlapping bands prevent definitive assertions in terms of speciation when compared to the experimental spectra. Lastly, these observations are likely to hold in higher order aluminate oligomers andmore » as such present a massive challenge toward understanding the crystallization mechanisms relevant to aluminum processing.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Washington State Univ., Pullman, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Washington River Protection Solutions, LLC, Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Univ. of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Contributing Org.:
IDREAM (Interfacial Dynamics in Radioactive Environments and Materials); Environmental Molecular Sciences Laboratory (EMSL)
OSTI Identifier:
1504422
Alternate Identifier(s):
OSTI ID: 1596344
Report Number(s):
PNNL-SA-132755
Journal ID: ISSN 1520-6106
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 122; Journal Issue: 29; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pouvreau, Maxime, Dembowski, Mateusz, Clark, Sue B., Reynolds, Jacob G., Rosso, Kevin M., Schenter, Gregory K., Pearce, Carolyn I., and Clark, Aurora E. Ab Initio Molecular Dynamics Reveal Spectroscopic Siblings and Ion Pairing as New Challenges for Elucidating Prenucleation Aluminum Speciation. United States: N. p., 2018. Web. doi:10.1021/acs.jpcb.8b04377.
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Pouvreau, Maxime, Dembowski, Mateusz, Clark, Sue B., Reynolds, Jacob G., Rosso, Kevin M., Schenter, Gregory K., Pearce, Carolyn I., & Clark, Aurora E. Ab Initio Molecular Dynamics Reveal Spectroscopic Siblings and Ion Pairing as New Challenges for Elucidating Prenucleation Aluminum Speciation. United States. https://doi.org/10.1021/acs.jpcb.8b04377
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Pouvreau, Maxime, Dembowski, Mateusz, Clark, Sue B., Reynolds, Jacob G., Rosso, Kevin M., Schenter, Gregory K., Pearce, Carolyn I., and Clark, Aurora E. Sun . "Ab Initio Molecular Dynamics Reveal Spectroscopic Siblings and Ion Pairing as New Challenges for Elucidating Prenucleation Aluminum Speciation". United States. https://doi.org/10.1021/acs.jpcb.8b04377. https://www.osti.gov/servlets/purl/1504422.
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@article{osti_1504422,
title = {Ab Initio Molecular Dynamics Reveal Spectroscopic Siblings and Ion Pairing as New Challenges for Elucidating Prenucleation Aluminum Speciation},
author = {Pouvreau, Maxime and Dembowski, Mateusz and Clark, Sue B. and Reynolds, Jacob G. and Rosso, Kevin M. and Schenter, Gregory K. and Pearce, Carolyn I. and Clark, Aurora E.},
abstractNote = {We report the characterization of prenucleation species is essential to understand crystallization mechanisms across many chemical systems and often involves the use of vibrational spectroscopy. Nowhere is this more evident than in the development of “green” aluminum processing technologies, where detailed understanding of the speciation of aluminum and its polynuclear analogues in highly alkaline, low water solutions is elusive. The aluminate anion Al(OH)4– predominates in alkaline conditions, yet equilibrium with dimeric species, either μ-oxo Al2O(OH)62– or di-μ-hydroxo Al2(OH)82–, can be assumed. Using ab initio molecular dynamics with full solvation and the presence of counterions, this work reconciles previous contradictory studies that had concluded only a single species under relevant solution conditions. We reveal that the two dimers are energetically separated by 2 kcal/mol in pure water but that the stability of each can be reversed by ion pairing expected in saturated salt solutions. Simulated Raman and IR spectra for each species (accounting for anharmonicity and the fluctuating solvating environment) provide the first proof that the considered species are “spectroscopic siblings”, whose multiple overlapping bands prevent definitive assertions in terms of speciation when compared to the experimental spectra. Lastly, these observations are likely to hold in higher order aluminate oligomers and as such present a massive challenge toward understanding the crystallization mechanisms relevant to aluminum processing.},
doi = {10.1021/acs.jpcb.8b04377},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 29,
volume = 122,
place = {United States},
year = {Sun Jun 24 00:00:00 EDT 2018},
month = {Sun Jun 24 00:00:00 EDT 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcb.8b04377
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Cited by: 26 works
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Figures / Tables:

Figure 1 Figure 1: AIMD snapshots of (a) Al(OH)4−, (b) Al2O(OH)62−, and (c) Al2(OH)82− and average Al−O bond lengths from the simulation trajectory. (b) Al−O bond lengths in the K2[Al2O(OH)6] crystal are in parentheses. (d,e) AIMD snapshots of the ion-paired species Na+· Al2O(OH)62− (with the second, separate Na+) and 2Na+··· Al2(OH)82−.
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    Works referencing / citing this record:

    PageRank as a collective variable to study complex chemical transformations and their energy landscapes
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    • The Journal of Chemical Physics, Vol. 150, Issue 13
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    Inference of principal species in caustic aluminate solutions through solid-state spectroscopic characterization
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    • Dembowski, Mateusz; Prange, Micah P.; Pouvreau, Maxime
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    Ion–ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH) 3 ) with sodium nitrite/nitrate
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    • Dembowski, Mateusz; Snyder, Michelle M.; Delegard, Calvin H.
    • Physical Chemistry Chemical Physics, Vol. 22, Issue 8
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