EPR and optical spectroscopy of structural phase transition in a Rb<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:msub><mml:mrow /><mml:mn>2</mml:mn></mml:msub></mml:math>NaYF<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:msub><mml:mrow /><mml:mn>6</mml:mn></mml:msub></mml:math>crystal

Falin, M. L.; Gerasimov, K. I.; Latypov, V. A.; Leushin, A. M.; Хайдуков, Н. М.

doi:10.1103/physrevb.87.115145

Cited by 12 publications

(4 citation statements)

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“…%) and 173 Yb ( I = 7 / 2 , 16.1 at. %) with significant hyperfine coupling in both of them, and large g -tensor anisotropy, so the resulting EPR spectra can also be quite complicated …”

Section: Methodsmentioning

confidence: 99%

“…37,38 In contrast, Yb 3+ is an S=1/2 ion, for which there is no ZFS; however, it has two magnetic isotopes, 171 Yb (I=1/2, 14.3 at%) and 173 Yb (I=7/2, 16.1 at%) with significant hyperfine coupling in both of them, and large g-tensor anisotropy , so the resulting EPR spectra can also be quite complicated. 39 The ZFS contribution depends on CF around the probe ion. As the 8 S 7/2 state cannot contribute to CF, ZFS in Gd 3+ ion originates entirely from the mixing of this ground state with the excited 6 P 7/2 and 6 D 7/2 states (that account for ca.…”

Section: Continuous Wave Epr Spectroscopymentioning

confidence: 99%

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In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids

et al. 2015

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Coordination polymers (CPs) of metal ions are central to a large variety of applications, such as catalysis and separations. These polymers frequently occur as amorphous solids that segregate from solution. The structural aspects of this segregation remain elusive due to the dearth of the spectroscopic techniques and computational approaches suitable for probing such systems. Therefore, there is a lacking of understanding of how the molecular building blocks give rise to the mesoscale architectures that characterize CP materials. In this study we revisit a CP phase formed in the extraction of trivalent lanthanide ions by diesters of the phosphoric acid, such as the bis(2-ethylhexyl)phosphoric acid (HDEHP). This is a well-known system with practical importance in strategic metals refining and nuclear fuel reprocessing. A CP phase, referred to as a "third phase", has been known to form in these systems for half a century, yet the structure of the amorphous solid is still a point of contention, illustrating the difficulties faced in characterizing such materials. In this study, we follow a deductive approach to solving the molecular structure of amorphous CP phases, using semiempirical calculations to set up an array of physically plausible models and then deploying a suite of experimental techniques, including optical, magnetic resonance, and X-ray spectroscopies, to consecutively eliminate all but one model. We demonstrate that the "third phase" consists of hexagonally packed linear chains in which the lanthanide ions are connected by three O-P-O bridges, with the modifying groups protruding outward, as in a bottlebrush. The tendency to yield linear polynuclear oligomers that is apparent in this system may also be present in other systems yielding the "third phase", demonstrating how molecular geometry directs polymeric assembly in hybrid materials. We show that the packing of bridging molecules is central to directing the structure of CP phases and that by manipulating the steric requirements of ancillary groups one can control the structure of the assembly.

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“…%) and 173 Yb ( I = 7 / 2 , 16.1 at. %) with significant hyperfine coupling in both of them, and large g -tensor anisotropy, so the resulting EPR spectra can also be quite complicated …”

Section: Methodsmentioning

confidence: 99%

Section: Continuous Wave Epr Spectroscopymentioning

confidence: 99%

In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids

et al. 2015

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“…The presence of negative (ie, imaginary) frequencies in all iodide elpasolites, and in a number of chloride/bromide elpasolites, suggests structural instability of those compounds. Indeed, there have been numerous reports of cubic to tetragonal phase transitions for the Cs 2 Na Ln Br 6 group, in the range from 316 K ( Ln = La) to 173 K ( Ln = Gd) 39 and in some hexafluoroelpasolites, such as Rb 2 NaYF 6 40‐43 and Cs 2 KMnF 6 44 …”

Section: Results Of Calculations and Discussionmentioning

confidence: 99%

“…The lines are the guides to the eye only [Color figure can be viewed at wileyonlinelibrary.com]instability of those compounds. Indeed, there have been numerous reports of cubic to tetragonal phase transitions for the Cs 2 NaLnBr 6 group, in the range from 316 K (Ln = La) to 173 K (Ln = Gd)39 and in some hexafluoroelpasolites, such as Rb 2 NaYF 6[40][41][42][43] and Cs 2 KMnF 6 44.…”

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confidence: 99%

Effects of chemical composition on the structural stability, elastic, vibrational, and electronic properties of Cs₂NaLnX₆ (Ln = La…Lu, X = F, Cl, Br, I) elpasolites

Yang

Yan

et al. 2020

J. Am. Ceram. Soc.

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Elpasolite crystals are very important materials, both from the applied and fundamental points of view. Those elpasolites, which contain rare earth ions with a high atomic number Z, are very much suitable for the low-cost high-performance gamma-ray detection, applications in medicine, food industry, nuclear energy production, processing, and detection of nuclear proliferation. The thermal and structural stabilities are important parameters required for detecting applications, because the performance conditions for such devices are usually very harsh. Since it is widely believed that elpasolites may have even better detection properties, the lack of systematic studies on the elpasolites and thus the unavailability of reliable data on their physical properties and trends in their variation caused by chemical composition considerably hinders search for more efficient new materials. Therefore, to fill in this gap and provide with all essential information about a large number of elpasolites crystals, for the first time, the structural stability, elastic, vibrational, and electronic properties of 60 cubic elpasolite Cs 2 NaLnX 6 (Ln = La, …, Lu, X = F, Cl, Br, I) crystals were consistently calculated in the framework of the same computational approach based on the density functional theory (DFT). Variation of all calculated parameters (such as the lattice constants, elastic constants, Debye temperature, normal vibrational modes frequencies, Mulliken effective charges, bond populations, and band gaps) across the considered groups of crystals was analyzed and several trends, which are important 1490 | WU et al.

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Application of Different Spectral Methods to Examine Structure of the Complexes Found in the Cycloaddition Reactions of 4-Trifluoromethylbenzonitrile Oxide to Olefins

et al. 2013

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EPR and optical spectroscopy of structural phase transition in a Rb2NaYF6crystal

Cited by 12 publications

References 49 publications

In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids

In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids

Effects of chemical composition on the structural stability, elastic, vibrational, and electronic properties of Cs₂NaLnX₆ (Ln = La…Lu, X = F, Cl, Br, I) elpasolites

Application of Different Spectral Methods to Examine Structure of the Complexes Found in the Cycloaddition Reactions of 4-Trifluoromethylbenzonitrile Oxide to Olefins

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EPR and optical spectroscopy of structural phase transition in a Rb2NaYF6crystal

Cited by 12 publications

References 49 publications

In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids

In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids

Effects of chemical composition on the structural stability, elastic, vibrational, and electronic properties of Cs2NaLnX6 (Ln = La…Lu, X = F, Cl, Br, I) elpasolites

Application of Different Spectral Methods to Examine Structure of the Complexes Found in the Cycloaddition Reactions of 4-Trifluoromethylbenzonitrile Oxide to Olefins

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Effects of chemical composition on the structural stability, elastic, vibrational, and electronic properties of Cs₂NaLnX₆ (Ln = La…Lu, X = F, Cl, Br, I) elpasolites