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

Vaughn, John S.; Lindsley, Donald H.; Nekvasil, Hanna; Hughes, John M.; Phillips, Brian L.

doi:10.1021/acs.jpcc.7b09912

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

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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:

^[1]; Lindsley, Donald H. ^[2]; Nekvasil, Hanna ^[2]; Hughes, John M. ^[3];

^[2]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
Stony Brook Univ., NY (United States). Dept. of Geosciences
Univ. of Vermont, Burlington, VT (United States). Dept. of Geology

Publication Date:: Fri Dec 08 00:00:00 EST 2017

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.

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                    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.  https://doi.org/10.1021/acs.jpcc.7b09912

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                    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.  https://doi.org/10.1021/acs.jpcc.7b09912.  https://www.osti.gov/servlets/purl/1465272.

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@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         = {Fri Dec 08 00:00:00 EST 2017},

  month        = {Fri Dec 08 00:00:00 EST 2017}

}

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