Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb2B10H10

Dimitrievska, Mirjana; Stavila, Vitalie; Soloninin, Alexei V.; Skoryunov, Roman V.; Babanova, Olga A.; Wu, Hui; Zhou, Wei; Tang, Wan Si; Faraone, Antonio; Tarver, Jacob D.; Trump, Benjamin A.; Skripov, Alexander V.; Udovic, Terrence J.

doi:10.1021/acs.jpcc.8b04385

Title: Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb₂B₁₀H₁₀

Abstract

The ordered monoclinic phase of the alkali-metal decahydro-closo-decaborate salt Rb₂B₁₀H₁₀ was found to be stable from about 250 K all the way up to an order-disorder phase transition temperature of ~762 K. The broad temperature range for this phase allowed for a detailed quasielastic neutron scattering (QENS) and nuclear magnetic resonance (NMR) study of the protypical B₁₀H₁₀^2- anion reorientational dynamics. The QENS and NMR combined results are consistent with an anion reorientational mechanism comprised of two types of rotational jumps expected from the anion geometry and lattice structure, namely, more rapid 90 degree jumps around the anion C₄ symmetry axis (e.g., with correlation frequencies of ~2.6 x 10¹⁰ s^-1 at 530 K) combined with order of magnitude slower orthogonal 180 degree reorientational flips (e.g., ~3.1 x 10⁹ s^-1 at 530 K) resulting in an exchange of the apical H (and apical B) positions. Each latter flip requires a concomitant 45 degree twist around the C₄ symmetry axis to preserve the ordered Rb₂B₁₀H₁₀ monoclinic structural symmetry. This result is consistent with previous NMR data for ordered monoclinic Na₂B₁₀H₁₀, which also pointed to two types of anion reorientational motions. The QENS-derived reorientational activation energies are 197(2) and 288(3) meV for the C₄more »« less

Authors:

^[1];

^[2]; Soloninin, Alexei V. ^[3];

^[3]; Babanova, Olga A. ^[3];

^[4]; Zhou, Wei ^[4]; Tang, Wan Si ^[5]; Faraone, Antonio ^[4]; Tarver, Jacob D. ^[1]; Trump, Benjamin A. ^[4];

^[3];

^[4]

National Renewable Energy Lab. (NREL), Golden, CO (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Russian Academy of Sciences (RAS), Ekaterinburg (Russian Federation)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; Univ. of Maryland, College Park, MD (United States); Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab.

Publication Date:: Mon Jun 11 00:00:00 EDT 2018

Research Org.:: Sandia National Lab. (SNL-CA), Livermore, CA (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office

OSTI Identifier:: 1507407

Alternate Identifier(s):: OSTI ID: 1476875

Report Number(s):: SAND-2019-3247J; NREL/JA-5900-72563
Journal ID: ISSN 1932-7447; 673701

Grant/Contract Number:: AC04-94AL85000; NA0003525; DMR-0944772; DMR-1508249; AC02-06CH1135; AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 27; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; activation energy; neutron scattering; nuclear magnetic resonance; rubidium compounds

Citation Formats


                    Dimitrievska, Mirjana, Stavila, Vitalie, Soloninin, Alexei V., Skoryunov, Roman V., Babanova, Olga A., Wu, Hui, Zhou, Wei, Tang, Wan Si, Faraone, Antonio, Tarver, Jacob D., Trump, Benjamin A., Skripov, Alexander V., and Udovic, Terrence J. Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb2B10H10.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.8b04385.

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                    Dimitrievska, Mirjana, Stavila, Vitalie, Soloninin, Alexei V., Skoryunov, Roman V., Babanova, Olga A., Wu, Hui, Zhou, Wei, Tang, Wan Si, Faraone, Antonio, Tarver, Jacob D., Trump, Benjamin A., Skripov, Alexander V., & Udovic, Terrence J. Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb2B10H10.  United States.  https://doi.org/10.1021/acs.jpcc.8b04385

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                    Dimitrievska, Mirjana, Stavila, Vitalie, Soloninin, Alexei V., Skoryunov, Roman V., Babanova, Olga A., Wu, Hui, Zhou, Wei, Tang, Wan Si, Faraone, Antonio, Tarver, Jacob D., Trump, Benjamin A., Skripov, Alexander V., and Udovic, Terrence J. Mon .  
"Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb2B10H10".  United States.  https://doi.org/10.1021/acs.jpcc.8b04385.  https://www.osti.gov/servlets/purl/1507407.

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@article{osti_1507407,

  title        = {Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb2B10H10},

  author       = {Dimitrievska, Mirjana and Stavila, Vitalie and Soloninin, Alexei V. and Skoryunov, Roman V. and Babanova, Olga A. and Wu, Hui and Zhou, Wei and Tang, Wan Si and Faraone, Antonio and Tarver, Jacob D. and Trump, Benjamin A. and Skripov, Alexander V. and Udovic, Terrence J.},

  abstractNote = {The ordered monoclinic phase of the alkali-metal decahydro-closo-decaborate salt Rb2B10H10 was found to be stable from about 250 K all the way up to an order-disorder phase transition temperature of ~762 K. The broad temperature range for this phase allowed for a detailed quasielastic neutron scattering (QENS) and nuclear magnetic resonance (NMR) study of the protypical B10H102- anion reorientational dynamics. The QENS and NMR combined results are consistent with an anion reorientational mechanism comprised of two types of rotational jumps expected from the anion geometry and lattice structure, namely, more rapid 90 degree jumps around the anion C4 symmetry axis (e.g., with correlation frequencies of ~2.6 x 1010 s-1 at 530 K) combined with order of magnitude slower orthogonal 180 degree reorientational flips (e.g., ~3.1 x 109 s-1 at 530 K) resulting in an exchange of the apical H (and apical B) positions. Each latter flip requires a concomitant 45 degree twist around the C4 symmetry axis to preserve the ordered Rb2B10H10 monoclinic structural symmetry. This result is consistent with previous NMR data for ordered monoclinic Na2B10H10, which also pointed to two types of anion reorientational motions. The QENS-derived reorientational activation energies are 197(2) and 288(3) meV for the C4 fourfold jumps and apical exchanges, respectively, between 400 and 680 K. Below this temperature range, NMR (and QENS) both indicate a shift to significantly larger reorientational barriers, for example, 485(8) meV for the apical exchanges. Finally, subambient diffraction measurements identify a subtle change in the Rb2B10H10 structure from monoclinic to triclinic symmetry as the temperature is decreased from around 250 to 210 K.},

  doi          = {10.1021/acs.jpcc.8b04385},

  journal      = {Journal of Physical Chemistry. C},

  number       = 27,

  volume       = 122,

  place        = {United States},

  year         = {Mon Jun 11 00:00:00 EDT 2018},

  month        = {Mon Jun 11 00:00:00 EDT 2018}

}

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https://doi.org/10.1021/acs.jpcc.8b04385

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Cited by: 6 works

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Figures / Tables:

Figure 1: The 298 K monoclinic ($P2$₁/$n$) Rb₂B₁₀H₁₀ structure from model refinement of the Rb2¹¹B₁₀H₁₀ SXRPD data based on DFT optimization of the structure reported in ref. 16. Magenta, green, and white spheres denote Rb, B, and H atoms, respectively.

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Title: Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb2B10H10

Abstract

Citation Formats

Figures / Tables:

Title: Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb₂B₁₀H₁₀