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Title: Complex F,Cl Apatite Solid Solution Investigated Using Multinuclear Solid-State NMR Methods

Abstract

In this paper, a series of synthetic F,Cl apatites with low hydroxyl content was investigated using 31P, 19F, and 35Cl solid-state magic angle spinning (MAS) NMR spectroscopic methods. 31P single-pulse (SP) NMR spectra show that for each composition the phosphate 31P chemical shift depends on occupancy of the nearest anion site for each composition. Overall the average chemical shift deviates from linear across the F/Cl series. For intermediate compositions 19F SP NMR spectra reveal complex, broadened spectral profiles that are not correlated to composition. 19F{ 35Cl} TRAPDOR results indicate that the spectral profiles do not reflect occupancy of F and Cl in adjacent column anion sites. We propose that the complex 19F lineshapes are principally due to broad distributions of 19F–Ca distances arising from displacement of F along the anion channel. Finally, approximate fluorine atomic positions are estimated based on 19F chemical shifts of alkaline earth fluoride salts, and the results are in good accord with those proposed for intermediate composition F,Cl apatites from XRD data.

Authors:
ORCiD logo [1];  [2];  [2];  [3]; ORCiD logo [2]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
  2. Stony Brook Univ., NY (United States). Dept. of Geosciences
  3. Univ. of Vermont, Burlington, VT (United States). Dept. of Geology
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Stony Brook Univ., NY (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1465272
Report Number(s):
LLNL-JRNL-742985
Journal ID: ISSN 1932-7447; 898089; TRN: US1902461
Grant/Contract Number:  
AC52-07NA27344; EAR 1249696
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 1; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Vaughn, John S., Lindsley, Donald H., Nekvasil, Hanna, Hughes, John M., and Phillips, Brian L. Complex F,Cl Apatite Solid Solution Investigated Using Multinuclear Solid-State NMR Methods. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b09912.
Vaughn, John S., Lindsley, Donald H., Nekvasil, Hanna, Hughes, John M., & Phillips, Brian L. Complex F,Cl Apatite Solid Solution Investigated Using Multinuclear Solid-State NMR Methods. United States. doi:10.1021/acs.jpcc.7b09912.
Vaughn, John S., Lindsley, Donald H., Nekvasil, Hanna, Hughes, John M., and Phillips, Brian L. Fri . "Complex F,Cl Apatite Solid Solution Investigated Using Multinuclear Solid-State NMR Methods". United States. doi:10.1021/acs.jpcc.7b09912. https://www.osti.gov/servlets/purl/1465272.
@article{osti_1465272,
title = {Complex F,Cl Apatite Solid Solution Investigated Using Multinuclear Solid-State NMR Methods},
author = {Vaughn, John S. and Lindsley, Donald H. and Nekvasil, Hanna and Hughes, John M. and Phillips, Brian L.},
abstractNote = {In this paper, a series of synthetic F,Cl apatites with low hydroxyl content was investigated using 31P, 19F, and 35Cl solid-state magic angle spinning (MAS) NMR spectroscopic methods. 31P single-pulse (SP) NMR spectra show that for each composition the phosphate 31P chemical shift depends on occupancy of the nearest anion site for each composition. Overall the average chemical shift deviates from linear across the F/Cl series. For intermediate compositions 19F SP NMR spectra reveal complex, broadened spectral profiles that are not correlated to composition. 19F{35Cl} TRAPDOR results indicate that the spectral profiles do not reflect occupancy of F and Cl in adjacent column anion sites. We propose that the complex 19F lineshapes are principally due to broad distributions of 19F–Ca distances arising from displacement of F along the anion channel. Finally, approximate fluorine atomic positions are estimated based on 19F chemical shifts of alkaline earth fluoride salts, and the results are in good accord with those proposed for intermediate composition F,Cl apatites from XRD data.},
doi = {10.1021/acs.jpcc.7b09912},
journal = {Journal of Physical Chemistry. C},
number = 1,
volume = 122,
place = {United States},
year = {2017},
month = {12}
}

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