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Title: Structure and Liquid Fragility in Sodium Carbonate

Abstract

In this paper, the relationship between local structure and dynamics is explored for molten sodium carbonate. A flexible fluctuating-charge model, which allows for changes in the shape and charge distribution of the carbonate molecular anion, is developed. The system shows the evolution of highly temperature-dependent complex low-dimensional structures which control the dynamics (and hence the liquid fragility). By varying the molecular anion charge distribution, the key interactions responsible for the formation of these structures can be identified and rationalized. Finally, an increase in the mean charge separation within the carbonate ions increases the connectivity of the emerging structures and leads to an increase in the system fragility.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [5];  [5];  [6];  [7]
+ Show Author Affiliations
  1. Univ. of Oxford (United Kingdom). Dept. of Chemistry. Physical and Theoretical Chemistry Lab.
  2. Univ. of São Paulo (Brazil). Lab. of Molecular Spectroscopy. Inst. of Chemistry
  3. Univ. College London (United Kingdom). Dept. of Chemistry
  4. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  5. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division; Materials Development Inc., Arlington Heights, IL (United States)
  6. Materials Development Inc., Arlington Heights, IL (United States)
  7. Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Materials Development Inc., Arlington Heights, IL (United States); Univ. of Oxford (United Kingdom)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Engineering and Physical Sciences Research Council (EPSRC)
OSTI Identifier:
1461315
Grant/Contract Number:  
AC02-06CH11357; SC0015241; EP/L015722/1
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 4; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wilson, Mark, Ribeiro, Mauro C. C., Wilding, Martin C., Benmore, Chris, Weber, J. K. R., Alderman, Oliver, Tamalonis, Anthony, and Parise, J. B. Structure and Liquid Fragility in Sodium Carbonate. United States: N. p., 2017. Web. doi:10.1021/acs.jpca.7b10712.
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Wilson, Mark, Ribeiro, Mauro C. C., Wilding, Martin C., Benmore, Chris, Weber, J. K. R., Alderman, Oliver, Tamalonis, Anthony, & Parise, J. B. Structure and Liquid Fragility in Sodium Carbonate. United States. https://doi.org/10.1021/acs.jpca.7b10712
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Wilson, Mark, Ribeiro, Mauro C. C., Wilding, Martin C., Benmore, Chris, Weber, J. K. R., Alderman, Oliver, Tamalonis, Anthony, and Parise, J. B. Fri . "Structure and Liquid Fragility in Sodium Carbonate". United States. https://doi.org/10.1021/acs.jpca.7b10712. https://www.osti.gov/servlets/purl/1461315.
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@article{osti_1461315,
title = {Structure and Liquid Fragility in Sodium Carbonate},
author = {Wilson, Mark and Ribeiro, Mauro C. C. and Wilding, Martin C. and Benmore, Chris and Weber, J. K. R. and Alderman, Oliver and Tamalonis, Anthony and Parise, J. B.},
abstractNote = {In this paper, the relationship between local structure and dynamics is explored for molten sodium carbonate. A flexible fluctuating-charge model, which allows for changes in the shape and charge distribution of the carbonate molecular anion, is developed. The system shows the evolution of highly temperature-dependent complex low-dimensional structures which control the dynamics (and hence the liquid fragility). By varying the molecular anion charge distribution, the key interactions responsible for the formation of these structures can be identified and rationalized. Finally, an increase in the mean charge separation within the carbonate ions increases the connectivity of the emerging structures and leads to an increase in the system fragility.},
doi = {10.1021/acs.jpca.7b10712},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 4,
volume = 122,
place = {United States},
year = {Fri Dec 15 00:00:00 EST 2017},
month = {Fri Dec 15 00:00:00 EST 2017}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpca.7b10712
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Cited by: 7 works
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Figures / Tables:

FIGURE 1 FIGURE 1: (a) A comparison of the melt X-ray total structure factors from the current experimental work obtained using containerless techniques under different levitating gases (the compositions of which are indicated in the legend) with thatpreviously obtained by Zarzycki. (b) The top two curves show the X-ray total structure factorsmore » from the present work obtained by experiment (purple line, levitated in Ar gas) and simulation (black line). Both of these curves are offset by one along the ordinate axis for clarity. The upper orange curve shows the effect of increasing the simulation temperature as described in the text. The remaining curves show the weighted contributions of the six partial structure factors (identified in the legend) to the simulation total structure factor.« less
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    CO3+1 network formation in ultra-high pressure carbonate liquids
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