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Title: Anticorrelated Contributions to Pre-edge Features of Aluminate Near-Edge X-ray Absorption Spectroscopy in Concentrated Electrolytes

Abstract

Ion pairing within complex solutions and electrolytes is a difficult phenomenon to measure and investigate, yet it has significant impact upon macroscopic processes, such as crystal formation. Traditional methods of detecting and characterizing ion pairing are sensitive to contact ion pairs, may require minimum concentrations that limit applicability, and can have difficulty in characterizing solutions with many components. Because of its element specificity and sensitivity to local environment, X-ray absorption near edge structure (XANES) is a promising tool for investigating ion pairing in complex solutions. In concentrated sodium aluminate solutions, a shift in the pre-edge shoulder correlated to sodium concentration is observed, and the physical origins of that shift are investigated using energy specific time-dependent density functional theory of subensembles obtained from ab initio molecular dynamics. Two transitions are found to contribute to the pre-edge feature, yet they are anticorrelated with respect to the sodium···aluminate distance. Unexpectedly, this causes Al XANES to be an effective probe for longer-range ion interactions than the traditional counterparts of NMR or vibrational spectroscopies. Given the nature of the transitions involved, this observation may be extended to other systems where ion–ion interactions dominate; however, a complete understanding of the contributing transitions is necessary for accuratemore » analysis of XANES pre-edge features in concentrated electrolytes.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
  2. Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1470495
Alternate Identifier(s):
OSTI ID: 1596340
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 10; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wildman, Andrew, Martinez-Baez, Ernesto, Fulton, John, Schenter, Gregory, Pearce, Carolyn, Clark, Aurora E., and Li, Xiaosong. Anticorrelated Contributions to Pre-edge Features of Aluminate Near-Edge X-ray Absorption Spectroscopy in Concentrated Electrolytes. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b00642.
Wildman, Andrew, Martinez-Baez, Ernesto, Fulton, John, Schenter, Gregory, Pearce, Carolyn, Clark, Aurora E., & Li, Xiaosong. Anticorrelated Contributions to Pre-edge Features of Aluminate Near-Edge X-ray Absorption Spectroscopy in Concentrated Electrolytes. United States. https://doi.org/10.1021/acs.jpclett.8b00642
Wildman, Andrew, Martinez-Baez, Ernesto, Fulton, John, Schenter, Gregory, Pearce, Carolyn, Clark, Aurora E., and Li, Xiaosong. Thu . "Anticorrelated Contributions to Pre-edge Features of Aluminate Near-Edge X-ray Absorption Spectroscopy in Concentrated Electrolytes". United States. https://doi.org/10.1021/acs.jpclett.8b00642. https://www.osti.gov/servlets/purl/1470495.
@article{osti_1470495,
title = {Anticorrelated Contributions to Pre-edge Features of Aluminate Near-Edge X-ray Absorption Spectroscopy in Concentrated Electrolytes},
author = {Wildman, Andrew and Martinez-Baez, Ernesto and Fulton, John and Schenter, Gregory and Pearce, Carolyn and Clark, Aurora E. and Li, Xiaosong},
abstractNote = {Ion pairing within complex solutions and electrolytes is a difficult phenomenon to measure and investigate, yet it has significant impact upon macroscopic processes, such as crystal formation. Traditional methods of detecting and characterizing ion pairing are sensitive to contact ion pairs, may require minimum concentrations that limit applicability, and can have difficulty in characterizing solutions with many components. Because of its element specificity and sensitivity to local environment, X-ray absorption near edge structure (XANES) is a promising tool for investigating ion pairing in complex solutions. In concentrated sodium aluminate solutions, a shift in the pre-edge shoulder correlated to sodium concentration is observed, and the physical origins of that shift are investigated using energy specific time-dependent density functional theory of subensembles obtained from ab initio molecular dynamics. Two transitions are found to contribute to the pre-edge feature, yet they are anticorrelated with respect to the sodium···aluminate distance. Unexpectedly, this causes Al XANES to be an effective probe for longer-range ion interactions than the traditional counterparts of NMR or vibrational spectroscopies. Given the nature of the transitions involved, this observation may be extended to other systems where ion–ion interactions dominate; however, a complete understanding of the contributing transitions is necessary for accurate analysis of XANES pre-edge features in concentrated electrolytes.},
doi = {10.1021/acs.jpclett.8b00642},
journal = {Journal of Physical Chemistry Letters},
number = 10,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}

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Works referencing / citing this record:

Modeling L 2,3 -edge X-ray absorption spectroscopy with linear response exact two-component relativistic time-dependent density functional theory
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