Characterization of the dynamics in the protonic conductor CsH₂PO₄ by ¹⁷O solid-state NMR spectroscopy and first-principles calculations: correlating phosphate and protonic motion

Journal of the American Chemical Society
Gunwoo KimClare P Grey

Abstract

(17)O NMR spectroscopy combined with first-principles calculations was employed to understand the local structure and dynamics of the phosphate ions and protons in the paraelectric phase of the proton conductor CsH2PO4. For the room-temperature structure, the results confirm that one proton (H1) is localized in an asymmetric H-bond (between O1 donor and O2 acceptor oxygen atoms), whereas the H2 proton undergoes rapid exchange between two sites in a hydrogen bond with a symmetric double potential well at a rate ≥10(7) Hz. Variable-temperature (17)O NMR spectra recorded from 22 to 214 °C were interpreted by considering different models for the rotation of the phosphate anions. At least two distinct rate constants for rotations about four pseudo C3 axes of the phosphate ion were required in order to achieve good agreement with the experimental data. An activation energy of 0.21 ± 0.06 eV was observed for rotation about the P-O1 axis, with a higher activation energy of 0.50 ± 0.07 eV being obtained for rotation about the P-O2, P-O3(d), and P-O3(a) axes, with the superscripts denoting, respectively, dynamic donor and acceptor oxygen atoms of the H-bond. The higher activation energy of the second process is most likely associated wit...Continue Reading

References

Nov 1, 1996·Journal of Magnetic Resonance. Series a·J P AmoureuxS Steuernagel
Apr 15, 1990·Physical Review. B, Condensed Matter·D Vanderbilt
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Sep 26, 2000·Journal of Magnetic Resonance·P A Beckmann, C Dybowski
Apr 20, 2001·Nature·S M HaileR B Merle
Nov 25, 2003·Science·Dane A BoysenSossina M Haile
Jul 25, 2006·Chemical Society Reviews·Sharon E Ashbrook, Mark E Smith
Mar 1, 2007·Faraday Discussions·Sossina M HaileTetsuya Uda
Oct 11, 2007·Journal of the American Chemical Society·Sharon E AshbrookStephen Wimperis
Feb 10, 2009·Journal of Magnetic Resonance·Robert L Vold, Gina L Hoatson
Sep 16, 2011·Journal of the American Chemical Society·Frédéric BlancClare P Grey
Nov 19, 2011·Science·Eric D Wachsman, Kang Taek Lee
Aug 11, 2012·Journal of the American Chemical Society·Xianqi KongGang Wu

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Citations

Jul 28, 2016·The Journal of Physical Chemistry. B·Eric G KeelerRobert G Griffin
Aug 20, 2016·Journal of the American Chemical Society·David M HalatClare P Grey
Apr 28, 2016·Chemical Communications : Chem Comm·Sharon E Ashbrook, David McKay
Mar 27, 2018·Chemistry : a European Journal·Martin MangstlJörn Schmedt Auf der Günne
Sep 5, 2019·Membranes·Ioannis GaragounisMichael Stoukides
Aug 5, 2017·Acta Crystallographica. Section E, Crystallographic Communications·Carla Larvor, Berthold Stöger
Mar 4, 2020·Nature Materials·Sacha FopAbbie C Mclaughlin
Oct 11, 2017·Journal of the American Chemical Society·Jeffrey D MartellJeffrey R Long

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Methods Mentioned

BETA
NMR
X-ray
neutron diffraction

Software Mentioned

CASTEP
EXPRESS
MAS

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