| 1. |
- Ma, G. B., et al.
(författare)
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Structure of the dimethyl sulfoxide solvated thallium(III) ion in solution and in the solid state
- 2001
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 40:25, s. 6432-6438
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Tidskriftsartikel (refereegranskat)abstract
- The structure and vibrational spectra of the dimethyl sulfoxide solvated thallium(III) ion have been studied in a dimethyl sulfoxide solution and in the solid state. X-ray crystallography shows a trigonal unit cell, space group R (3) over bar (No. 148), for the [TI(dmso)(6)](ClO4)(3) Compound with Z = 3, a = b = 11.9764(13) [11.8995(9)] Angstrom, c = 20.802(2) [20.467(2)] Angstrom, and V = 2584.0(5) [2509.9(4)] Angstrom (3) at 295 [150] K. The crystal structure comprises a highly symmetric hexakis(dimethyl sulfoxide)thallium(III) ion, with thallium in a 3 symmetry site and a TI-O bond distance of 2.224(3) Angstrom at 295 K. The octahedral TlO6 kernel is compressed along the threefold axis with an O-Tl-O bond angle of 96.20(11)degrees. The Tl-O-S bond angle of 120.7(2)degrees corresponds to a Tl . . .S distance of 3.292(2) Angstrom. One perchlorate ion centered on the (3) over bar axis was described by a statistically disordered model. A low-temperature EXAFS study (10 K) resulted in the TI-O and Tl . . .S distances of 2.221(4) and 3.282(6) Angstrom, respectively, consistent with a Tl-O-S bond angle of 120(1)degrees. The low Debye-Waller factors confirm a regular coordination without the disorder of the dimethyl sulfoxide ligands, which would have resulted from the alternative choice of space group R3 for the crystal structure. Raman and infrared spectra have been recorded and assigned, with the bands at 435 and 447 cm(-1) corresponding to the vibrational frequency of the symmetric and asymmetric TI-O stretching modes, respectively. EXAFS data of a 0.5 mol dm(-3) thallium(III) trifluoromethanesulfonate in a dimethyl sulfoxide solution were consistent with that of a hexasolvated ion with mean Tl-O and Tl . . .S distances of 2.22(1) and 3.33(2) Angstrom, respectively, which correspond to a mean Tl-O-S bond angle of 124(2)degrees. The anomalously large disorder parameter for the TI-O distances is consistent with a weal, pseudo-Jahn-Teller effect. The Tl-205, C-13, and H-1 NMR spectra of the complex in solution show single signals at 1886, 39.5, and 2.3 ppm, respectively.
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| 2. |
- Zubkov, V. G., et al.
(författare)
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Structural, vibrational, electronic, and luminescence properties of the cyclotetravanadates A(2)M(VO3)(4) (A=Na,Ag; M=Ca,Sr)
- 2008
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 77, s. 174113-
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Tidskriftsartikel (refereegranskat)abstract
- The physical properties of the family of cyclotetravanadates A(2)M(VO3)(4), where A=Na,Ag and M=Ca,Sr, have been studied by means of x-ray powder diffraction, neutron diffraction, electron diffraction, infrared, Raman, NMR, photoexcitation and pulse cathode beam excitation, and x-ray photoelectron spectroscopies, and band structure calculations. The differences between the structural, vibrational, luminescence, and electronic properties of the alkali metal-containing [Na2Ca(VO3)(4) and Na2Sr(VO3)(4)] and the d metal-containing cyclotetravanadates [Ag2Ca(VO3)(4) and Ag2Sr(VO3)(4)] are analyzed. Na2Ca(VO3)(4), Ag2Ca(VO3)(4), Na2Sr(VO3)(4), and Ag2Sr(VO3)(4) have tetragonal structures, P4/nbm, with a=10.438 49(6), 10.445 24(5), 10.634 49(4), and 10.625 74(6), and c=4.938 73(5), 4.968 45(5), 4.962 05(4), and 4.979 30(4) angstrom, respectively. The main structural feature of A(2)M(VO3)(4) is the tetracyclic [V4O12] units. The hybridized O 2p-V 3d states of the tetracyclic [V4O12] units have a dominant influence on the electronic structure of these compounds. The compounds are semiconducting with a local density approximation band gap increasing, from 1.85 eV for Ag2Ca(VO3)(4) to 3.02 eV for Na2Ca(VO3)(4). The prospects of these compounds as advanced materials for detectors of photon and corpuscular radiation as well as for color correction of light emission sources such as lamp and light emitting diode sources are discussed.
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| 3. |
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| 4. |
- Risberg, Emiliana, Damian, et al.
(författare)
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Sulfur X-ray absorption and vibrational spectroscopic study of sulfite, sulfur dioxide and sulfonate solutions, and of the substituted sulfonate ions X3CSO3- (X = H, Cl, F)
- 2007
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 46:20, s. 8332-8348
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Tidskriftsartikel (refereegranskat)abstract
- Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra have been recorded and the S(1s) electron excitations evaluated by means of density functional theory−transition potential (DFT−TP) calculations to provide insight into the coordination, bonding, and electronic structure. The XANES spectra for the various species in sulfur dioxide and aqueous sodium sulfite solutions show considerable differences at different pH values in the environmentally important sulfite(IV) system. In strongly acidic (pH < 1) aqueous sulfite solution the XANES spectra confirm that the hydrated sulfur dioxide molecule, SO2(aq), dominates. The theoretical spectra are consistent with an OSO angle of 119° in gas phase and acetonitrile solution, while in aqueous solution hydrogen bonding reduces the angle to 116°. The hydration affects the XANES spectra also for the sulfite ion, SO32-. At intermediate pH (4) the two coordination isomers, the sulfonate (HSO3-) and hydrogen sulfite (SO3H-) ions with the hydrogen atom coordinated to sulfur and oxygen, respectively, could be distinguished with the ratio HSO3-:SO3H- about 0.28:0.72 at 298 K. The relative amount of HSO3- increased with increasing temperature in the investigated range from 275 to 343 K. XANES spectra of sulfonate, methanesulfonate, trichloromethanesulfonate, and trifluoromethanesulfonate compounds, all with closely similar S−O bond distances in tetrahedral configuration around the sulfur atom, were interpreted by DFT−TP computations. The energy of their main electronic transition from the sulfur K-shell is about 2478 eV. The additional absorption features are similar when a hydrogen atom or an electron-donating methyl group is bonded to the −SO3 group. Significant changes occur for the electronegative trichloromethyl (Cl3C−) and trifluoromethyl (F3C−) groups, which strongly affect the distribution especially of the π electrons around the sulfur atom. The S−D bond distance 1.38(2) Å was obtained for the deuterated sulfonate (DSO3-) ion by Rietveld analysis of neutron powder diffraction data of CsDSO3. Raman and infrared absorption spectra of the CsHSO3, CsDSO3, H3CSO3Na, and Cl3CSO3Na·H2O compounds and Raman spectra of the sulfite solutions have been interpreted by normal coordinate calculations. The C−S stretching force constant for the trichloromethanesulfonate ion obtains an anomalously low value due to steric repulsion between the Cl3C− and −SO3 groups. The S−O stretching force constants were correlated with corresponding S−O bond distances for several oxosulfur species.
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| 5. |
- Tyutyunnik, A. P., et al.
(författare)
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CRYSTAL STRUCTURE AND VIBRATIONAL SPECTRA OF M[VO(2)(SeO(4))(H(2)O)(2)]center dot H(2)O (M = K, Rb, NH(4))
- 2011
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Ingår i: Journal of Structural Chemistry. - 0022-4766 .- 1573-8779. ; 52:2, s. 350-357
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Tidskriftsartikel (refereegranskat)abstract
- By the hydration of MVO(SeO(4))(2) with saturated water vapors at room temperature a series of isostructural complex compounds of vanadium(V) of the composition M[VO(2)(SeO(4))(H(2)O)(2)]center dot H(2)O (K, Rb, NH(4)) are synthesized and their physicochemical properties are studied. Based on the X-ray and neutron diffraction data, it is found that their crystal structure is composed of VO(6) octahedra linked in infinite chains by bridging SeO(4) tetrahedra. Each of the VO(6) octahedra has two short terminal V-O bonds forming a bent dioxovanadium group VO(2)(+). Two water molecules are coordinated by vanadium and one molecule is out of the first coordination sphere in the interchain space. The vibrational spectra of the studied compounds are completely consistent with their structural features.
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| 6. |
- Vybornov, A., et al.
(författare)
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Chronological problems with neolithization of the northern caspian sea area and the forest-steppe povolzhye region
- 2012
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Ingår i: Radiocarbon. - 0033-8222 .- 1945-5755. ; 54:3-4, s. 795-799
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Tidskriftsartikel (refereegranskat)abstract
- Steppe and forest-steppe areas of the Povolzhye area (Caucasus and central Asia) bear much interest for the Neolithic in connection with the productive economy of the region at the time. Recent data have allowed correction of the region's chronology. A number of C-14 dates denote the existence of the Neolithic in this territory as early as the 5th to 6th millennium BP. However, some questions are still under debate and require further data to clarify.
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