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

Journal Article · · Journal of Physical Chemistry Letters
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)
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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. Finally, 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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; AC05-76RL01830
OSTI ID:
1470495
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 10 Vol. 9; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Modeling L 2,3 -edge X-ray absorption spectroscopy with linear response exact two-component relativistic time-dependent density functional theory journal June 2019

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