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Rhodium(III) speciation in concentrated nitric acid solutions / D. Vasilchenko [et al.] // Eur. J. Inorg. Chem. - 2016. - Vol. 2016, Is. 23. - P. 3822-3828, DOI 10.1002/ejic.201600523. - Cited References:31. - This work was supported by the Russian Foundation for Basic Research (grant number 16-03-00549 A). D. V. thanks the Ministry for Education and Science of the Russian Federation for the award of a President of the Russian Federation for Young Scientists Fellowship. . - ISSN 1434-1948. - ISSN 1099-0682

РУБ Chemistry, Inorganic & Nuclear
Рубрики:
MAGNETIC-RESONANCE
   FISSION PLATINOIDS
   AQUEOUS-SOLUTIONS
   PT-195 NMR
   RH(III)
   SPECTROSCOPY
   CHEMISTRY
   DISSOCIATION
   PLATINUM(IV)
   COMPLEXES
Кл.слова (ненормированные):
Rhodium -- NMR spectroscopy -- Nitrates
Аннотация: The interaction of rhodium(III) aqua ions with nitrate ions in 3–16 m nitric acid solutions has been studied by 103Rh and 15N NMR and Raman spectroscopy. The mononuclear complexes [Rh(H2O)6–n(NO3)n]3–n (n = 1–4) were found to be the only form of rhodium(III) existing in the solutions with the metal concentration in the range 0.2–1.3 m. The dynamics of the H2O → NO3– substitution process was studied at 80 °C. An increase in the average number of nitrate groups bonded to rhodium with increasing concentration of nitric acid was also determined. The fine crystalline salt Rb4trans-[Rh(H2O)2(NO3)4][Rh(NO3)6] was obtained by solvothermal concentration of the rhodium nitric acid solution on addition of rubidium nitrate. The structure of the salt was solved by the powder X-ray diffraction method, with monodentate coordination of nitrato ligands found for both the [Rh(NO3)6]3– and trans-[Rh(H2O)2(NO3)4]– anions.

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Держатели документа:
Russian Acad Sci, Nikolaev Inst Inorgan Chem, Siberian Branch, Novosibirsk 630090, Russia.
Novosibirsk State Univ, Novosibirsk 630090, Russia.
RAS, Inst Chem & Chem Technol, SB, Krasnoyarsk 660049, Russia.
RAS, Kirensky Inst Phys, SB, Krasnoyarsk 660036, Russia.
Siberian Fed Univ, 79 Svobodny Pr, Krasnoyarsk 660041, Russia.

Доп.точки доступа:
Vasilchenko, D.; Vorob'eva, S.; Tkachev, S.; Baidina, I. A.; Belyaev, A.; Korenev, S.; Solovyov, L.; Vasiliev, A. D.; Васильев, Александр Дмитриевич; Russian Foundation for Basic Research [16-03-00549 A]; Ministry for Education and Science of the Russian Federation
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    Structural and X-ray spectroscopy studies of Pb1-xBax(NO3)2 solid solutions / L. I. Isaenko [et al.] // J. Solid State Chem. - 2019. - Vol. 277. - P. 786-792, DOI 10.1016/j.jssc.2019.07.047. - Cited References: 37. - This work was done on state assignment of IGM SB RAS, Ministry of Science and Higher Education of the Russian Federation and was supported by Russian Foundation for Basic Research (grant No. 18-32-00359). . - ISSN 0022-4596
   Перевод заглавия: Структурные и рентгеноспектральные исследования твердого раствора Pb1-xBax(NO3)2
Кл.слова (ненормированные):
Crystal growth -- Crystal structure -- Nitrates -- Electronic structure -- XPS
Аннотация: Pb0.75(3)Ba0.25(3)(NO3)2, Pb0.68(3)Ba0.32(3)(NO3)2, Ba0.58(3)Pb0.42(3)(NO3)2, Ba0.81(3)Pb0.19(3)(NO3)2 crystals were grown for the first time when studying the Pb(NO3)2–Ba(NO3)2–H2O system. The crystals were grown in water solution with different relation of Pb(NO3)2 and Ba(NO3)2. It was found that series of solid solutions were formed by interaction of simple Pb(NO3)2 and Ba(NO3)2 compounds with a slow increase of volume and cell parameters from pure lead nitrate to pure barium nitrate. The crystal structure of all obtained Pb1-xBax(NO3)2 crystals belong to a cubic space group Pa-3. In these structures, Pb and Ba cations have the same coordination number 12, but different ionic radii (1.49 and 1.61 Å, respectively), anionic group is an equilateral triangle with O–O–O angle of 60° and O–O bond lengths ranging from 2.1305(8) to 2.2585(7) Å. The Pb2+ ion has a lone pair of electrons that are likely to be stereochemically active in these solid solutions leading to a significant amount of local disorder which explains the spread in the lattice parameters. The Pb1-xBax(NO3)2 solid solutions were characterized by X-ray photoelectron spectroscopy (XPS) by measuring the binding energies of the core-levels of constituting atoms and the shapes of the valence band. The XPS measurements indicate that the substitution of Pb for Ba does not cause changes in the charge states of the atoms constituting the Pb1-xBax(NO3)2 crystals. Matching the XPS valence-band spectra and the X-ray emission O Kα bands on a common energy scale indicates that the principal contributions of O 2p states occur at the top of the valence band of the crystals under study with also their substantial input in the upper and central portions of the band.

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Держатели документа:
Novosibirsk State University, Novosibirsk, 630090, Russian Federation
V.S. Sobolev Institute of Geology and Mineralogy, SB RAS, Novosibirsk, 630090, Russian Federation
Frantsevych Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanivsky Street, Kyiv, UA-03142, Ukraine
Kirensky Institute of Physics Federal Research Center KSC SB RAS, Krasnoyarsk, 660036, Russian Federation

Доп.точки доступа:
Isaenko, L. I.; Korzhneva, K. E.; Khyzhun, O. Y.; Molokeev, M. S.; Молокеев, Максим Сергеевич; Goloshumova, A. A.; Tarasova, A. Y.
}
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    Single crystal growth and the electronic structure of Rb2Na(NO3)3: Experiment and theory / K. E. Korzhneva, V. L. Bekenev, O. Y. Khyzhun [et al.] // J. Solid State Chem. - 2021. - Vol. 294. - Ст. 121910, DOI 10.1016/j.jssc.2020.121910. - Cited References: 54. - This work was done on state assignment of IGM SB RAS, Ministry of Science and Higher Education of the Russian Federation; NSU BCH-2020-0036-4 (10988) (XRD analysis), and was supported by Russian Foundation for Basic Research (grants Nos. 18-32-00359 , 19-42-540012) . - ISSN 0022-4596
   Перевод заглавия: Рост монокристалла и электронная структура Rb2Na(NO3)3: эксперимент и теория
Кл.слова (ненормированные):
Double nitrates -- Crystal growth -- Electronic structure -- Nonlinear optical materials -- X-ray photoelectron spectroscopy
Аннотация: Rb2Na(NO3)3 crystals demonstrate nonlinear optical properties and can be used as a converter of laser radiation in the shortwave region. The crystals were grown in the present work by the Bridgman–Stockbarger method in a ratio of 75 wt%(RbNO3) and 25 wt%(NaNO3). After the growth, a transparent centimeter size single crystal (6 cm long) was obtained for the first time that is very important for its practical application. The unit cell volume of double Rb2Na(NO3)3 nitrate is intermediate between the cell volumes of simple rubidium and sodium nitrates, RbNO3 and NaNO3. Electronic structure of Rb2Na(NO3)3 was studied in the present work from both experimental and theoretical viewpoints. In particular, employing X-ray photoelectron spectroscopy, we have measured binding energies of core electrons and energy distribution of the electronic states within the valence band region of the Rb2Na(NO3)3 crystal and established rather big binding energies for N 1s and O 1s core-level electrons. The bombardment of middle-energy Ar+ ions induces transformation of some nitrogen atoms of the analyzing topmost layers of the Rb2Na(NO3)3 crystal surface from the NO3– group to the NO2– group. To explore in detail the filling of the valence band of Rb2Na(NO3)3 by electronic states associated with constituting atoms, we use first-principles calculations within a density functional theory (DFT) framework. The DFT calculations reveal that O 2p states are the principal contributors to the valence band bringing the main input in its upper portion. The theoretical finding is supported experimentally by fitting the X-ray photoelectron valence band spectrum and the X-ray emission O Kα band on the total energy scale. The conduction band bottom of Rb2Na(NO3)3 is composed by unoccupied O 2p and N 2p states in almost equal proportion.

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Держатели документа:
Novosibirsk State University, Novosibirsk, 630090, Russian Federation
V.S. Sobolev Institute of Geology and Mineralogy, SB RAS, Novosibirsk, 630090, Russian Federation
Frantsevych Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanovsky StreetKyiv UA-03142, Ukraine
Kirensky Institute of Physics Federal Research Center KSC SB RAS, Krasnoyarsk, 660036, Russian Federation
Department of Physics, Far Eastern State Transport University, Khabarovsk, 680021, Russian Federation

Доп.точки доступа:
Korzhneva, K. E.; Bekenev, V. L.; Khyzhun, O. Y.; Goloshumova, A. A.; Tarasova, A. Y.; Molokeev, M. S.; Молокеев, Максим Сергеевич; Isaenko, L. I.; Kurus, A. F.
}
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