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Title: Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure

Abstract

This paper discusses our attempt to synthesize higher oxidation forms of cesium fluoride by pressurizing cesium fluoride in a fluorine-rich environment created via the x-ray decomposition of potassium tetrafluoroborate. This was done in order to confirm recent theoretical predictions of higher oxidation forms of CsFn. We discuss the development of a technique to produce molecular fluorine in situ via useful hard x-ray photochemistry, and the attempt to utilize this technique to form higher oxidation states of cesium fluoride. In order to verify the formation of the novel stoichiometric species of CsFn. X-ray Absorption Near Edge Spectroscopy (XANES) centered on the cesium K-edge was performed to probe the oxidation state of cesium as well as the local molecular coordination around Cs.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCESNSFDOE-NNSA
OSTI Identifier:
1409108
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physics. Conference Series; Journal Volume: 950; Journal Issue: 11, 2017; Conference: Madrid, Spain
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sneed, D., Pravica, M., Kim, E., Chen, N., Park, C., and White, M. Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure. United States: N. p., 2017. Web. doi:10.1088/1742-6596/950/4/042055.
Sneed, D., Pravica, M., Kim, E., Chen, N., Park, C., & White, M. Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure. United States. doi:10.1088/1742-6596/950/4/042055.
Sneed, D., Pravica, M., Kim, E., Chen, N., Park, C., and White, M. Sun . "Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure". United States. doi:10.1088/1742-6596/950/4/042055.
@article{osti_1409108,
title = {Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure},
author = {Sneed, D. and Pravica, M. and Kim, E. and Chen, N. and Park, C. and White, M.},
abstractNote = {This paper discusses our attempt to synthesize higher oxidation forms of cesium fluoride by pressurizing cesium fluoride in a fluorine-rich environment created via the x-ray decomposition of potassium tetrafluoroborate. This was done in order to confirm recent theoretical predictions of higher oxidation forms of CsFn. We discuss the development of a technique to produce molecular fluorine in situ via useful hard x-ray photochemistry, and the attempt to utilize this technique to form higher oxidation states of cesium fluoride. In order to verify the formation of the novel stoichiometric species of CsFn. X-ray Absorption Near Edge Spectroscopy (XANES) centered on the cesium K-edge was performed to probe the oxidation state of cesium as well as the local molecular coordination around Cs.},
doi = {10.1088/1742-6596/950/4/042055},
journal = {Journal of Physics. Conference Series},
number = 11, 2017,
volume = 950,
place = {United States},
year = {Sun Oct 01 00:00:00 EDT 2017},
month = {Sun Oct 01 00:00:00 EDT 2017}
}
  • In situ x-ray diffraction measurements of cesium azide (CsN{sub 3}) were performed at high pressures of up to 55.4 GPa at room temperature. Three phase transitions were revealed as follows: tetragonal (I4/mcm, Phase II) {yields} monoclinic (C2/m, Phase III) {yields} monoclinic (P2{sub 1}/m or P2{sub 1}, Phase IV) {yields} triclinic (P1 or P1{sup -}, Phase V), at 0.5, 4.4, and 15.4 GPa, respectively. During the II-III phase transition, CsN{sub 3} keeps its layered structure and the azide anions rotate obviously. The compressibility of Phase II is dominated by the repulsions between azide anions. The deformation of unit cell is isotropicmore » in Phases II and IV and anisotropic in Phase III. With increasing pressures, the monoclinic angle increases in Phase III and then becomes stable in Phase IV. The bulk moduli of Phases II, III, IV, and V are determined to be 18 {+-} 4, 20 {+-} 1, 27 {+-} 1 and 34 {+-} 1 GPa, respectively. The ionic character of alkali azides is found to play a key role in their pressure-induced phase transitions.« less
  • We have successfully loaded H{sub 2} into a diamond anvil cell at high pressure using the synchrotron x-ray induced decomposition of NH{sub 3}BH{sub 3}. In a second set of studies, radiation-assisted release of O{sub 2} from KCLO{sub 3}, H{sub 2} release from NH{sub 3}BH{sub 3}, and reaction of these gases in a mixture of the reactants to form liquid water using x-rays at ambient conditions was observed. Similar observations were made using a KCLO{sub 3} and NaBH{sub 4} mixture. Depending on reaction conditions, an explosive or far slower reaction producing water was observed.
  • We have successfully loaded H{sub 2} into a diamond anvil cell at high pressure using the synchrotron x-ray induced decomposition of NH{sub 3}BH{sub 3}. In a second set of studies, radiation-assisted release of O{sub 2} from KCLO{sub 3}, H{sub 2} release from NH{sub 3}BH{sub 3}, and reaction of these gases in a mixture of the reactants to form liquid water using x-rays at ambient conditions was observed. Similar observations were made using a KCLO{sub 3} and NaBH{sub 4} mixture. Depending on reaction conditions, an explosive or far slower reaction producing water was observed.
  • The local phonon density of states (DOS) at the Sn site in tin monoxide (SnO) is studied at pressures up to 8 GPa with 119Sn nuclear resonant inelastic x-ray scattering (NRIXS) of synchrotron radiation at 23.88 keV. The preferred orientation (texture) of the SnO crystallites in the investigated samples is used to measure NRIXS spectra preferentially parallel and almost perpendicular to the c axis of tetragonal SnO. A subtraction method is applied to these NRIXS spectra to produce projected local Sn DOS spectra as seen parallel and perpendicular to the c axis of SnO. These experimentally obtained local Sn DOSmore » spectra, both in the polycrystalline case as well as projected parallel and perpendicular to the c axis, are compared with corresponding theoretical phonon DOS spectra, derived from dispersion relations calculated with a recently developed shell model. Comparison between the experimental projected Sn DOS spectra and the corresponding theoretical DOS spectra enables us to follow the pressure-induced shifts of several acoustic and optic phonon modes. While the principal spectral features of the experimental and theoretical phonon DOS agree well at energies above 10 meV, the pressure behavior of the low-energy part of the DOS is not well reproduced by the theoretical calculations. In fact, they exhibit, in contrast to the experimental data, a dramatic softening of two low-energy modes, their energies approaching zero around 2.5 GPa, clearly indicating the limitations of the applied shell model. These difficulties are obviously connected with the complex Sn-O and Sn-Sn bindings within and between the Sn-O-Sn layers in the litharge structure of SnO. We derived from the experimental and theoretical DOS spectra a variety of elastic and thermodynamic parameters of the Sn sublattice, such as the Lamb-M{umlt o}ssbauer factor, the mean force constant, and Debye temperatures, as well as the vibrational contributions to the Helmholtz free energy, specific heat, entropy, and internal energy. We found, in part, good agreement between these values, for instance, for the Gr{umlt u}neisen parameters for some selected phonon modes, especially for some optical modes studied recently by Raman spectroscopy. We discuss in detail a possible anisotropy in the elastic parameters resulting from the litharge-type structure of SnO, for instance for the Lamb-M{umlt o}ssbauer factor, where we can compare with existing data from {sup 119}Sn-M{umlt o}ssbauer spectroscopy.« less
  • The local phonon density of states (DOS) at the Sn site in tin monoxide (SnO) is studied at pressures up to 8 GPa with {sup 119}Sn nuclear resonant inelastic x-ray scattering (NRIXS) of synchrotron radiation at 23.88 keV. The preferred orientation (texture) of the SnO crystallites in the investigated samples is used to measure NRIXS spectra preferentially parallel and almost perpendicular to the c axis of tetragonal SnO. A subtraction method is applied to these NRIXS spectra to produce projected local Sn DOS spectra as seen parallel and perpendicular to the c axis of SnO. These experimentally obtained local Snmore » DOS spectra, both in the polycrystalline case as well as projected parallel and perpendicular to the c axis, are compared with corresponding theoretical phonon DOS spectra, derived from dispersion relations calculated with a recently developed shell model. Comparison between the experimental projected Sn DOS spectra and the corresponding theoretical DOS spectra enables us to follow the pressure-induced shifts of several acoustic and optic phonon modes. While the principal spectral features of the experimental and theoretical phonon DOS agree well at energies above 10 meV, the pressure behavior of the low-energy part of the DOS is not well reproduced by the theoretical calculations. In fact, they exhibit, in contrast to the experimental data, a dramatic softening of two low-energy modes, their energies approaching zero around 2.5 GPa, clearly indicating the limitations of the applied shell model. These difficulties are obviously connected with the complex Sn-O and Sn-Sn bindings within and between the Sn-O-Sn layers in the litharge structure of SnO. We derived from the experimental and theoretical DOS spectra a variety of elastic and thermodynamic parameters of the Sn sublattice, such as the Lamb-Moessbauer factor, the mean force constant, and Debye temperatures, as well as the vibrational contributions to the Helmholtz free energy, specific heat, entropy, and internal energy. We found, in part, good agreement between these values, for instance, for the Grueneisen parameters for some selected phonon modes, especially for some optical modes studied recently by Raman spectroscopy. We discuss in detail a possible anisotropy in the elastic parameters resulting from the litharge-type structure of SnO, for instance for the Lamb-Moessbauer factor, where we can compare with existing data from {sup 119}Sn-Moessbauer spectroscopy.« less